The Kaduna State Governor, Ubersani, today met with the old student of the Federal Government College Kaduna over the annexation of the college land by the former governor, LRF's administration. The old student under the auspices of Unity School's Old Student Association and Federal Government College Kaduna had last Saturday staged a protest at the college premises calling on Governor Sani to restore the college land and next by the LRF's administration. The governor showed the old students that all walk at the site will be halted until he personally pays a visit to the school to assess the situation after which dialogue between the government and college stake orders will continue. Federal Government College Kaduna happens to be one of the schools that we realize that they were very vulnerable because of the allocations that is close to the river and we have instances of a lot of kidnappings around that vicinity and the community. But now that they came, I also listened to their complaint and I believe we need to also go back and look at the situation. We are still protesting because our meeting was not conclusive. Our interest as you saw since is that public education in Nigeria should be protected. The notification button so you get notified about fresh news updates.


What's going on everybody? Got Kyle and Matt here relating to sports cards. We are ripping 2023. This is top scrim update series hobby six box case number eight have Angelo D with the Mets Anthony R with the Astros. Anthony S has Rockies. RBB has the Mariners. We've got Benjamin T with the Jays and Giants. Brad T has D-backs. Brian S has Guardians. We've got Christopher S with the Dodgers. Daisuke T has the Braves. Eric R has the Orioles Red Sox and Angels. Gary A with the Pirates. Giancarlo F twins. James J has the Marlins. We have Jason W with the Royals. We've got JR with the Rangers. We've got Junghunt L with the Cubs. Liwei H has the A's in the Phillies. Matthew B with the Yankees. Ray G has Nationals Rays. Ramaris has the Cardinals. We've got Tai W with the Tigers. Tim W has Brewers. Tim L has the Padres. Timothy M with the Reds and Tom J with the White Sox. Alrighty guys good luck on this one. Again we are sold out on the daytime if you guys want to get some group breaks going today. Check the break schedule for tonight with Sam starting at five o'clock. Sam and Jake will get going on some soccer or not soccer. They have Star Wars, baseball, basketball, and football tonight. A good one there. I would definitely win this scholarship. The Dr. Pepper. Absolutely man I'm hitting every single one. I'm hitting every single one. No question. Alrighty good luck here guys. Top Scrum update hobby. We'll do our Jumbo Divisions case next. Come on debut patch. debut redemption. It's about that time. We'll do all the uh we'll get all the cards out here first guys and we'll start going through the boxes individually. A little easier way to do it here. University of Pennsylvania. How's everyone doing today? Been a little quiet since uh Texas started dominating. Also since two o'clock. Yep since M&M concerts started as well. Can't hard to compete with M&M. Hard to compete with M&M. The Jason Giants. If you are Benjamin T then yes. If you are Benjamin T then yes indeed. Good luck sir. Let's see what we got. They're replaying the event tonight. Oh okay so maybe we will have some downtime there. They're redoing the event. Okay okay. Oh no people are getting tattoos now Joshua. Guess I'm not surprised. Guess I'm not surprised. Yeah so if you're Benjamin T you do have the uh Jays and Giants at five and eleven. Okay doing it three times today. All right all right. It's kind of surprising. Alrighty good luck here guys. Box one. Louis Sarayas Refractor. Starting off with an aqua that's going to be Joey Wendell. Joey Wendell to $199 on the aqua. What's going on Dylan? Oscar Coloss he told me he doesn't want to dude. That's not true. He directly said that. Garrett Cole. Well we're told that it's at five and eleven today too so. They're redoing it. Yes we'll get back for the next uh. Like some multi really? Okay all right all right all right. It's insane but we had to come give us the give us the rundown. There's our auto going to be Jose Cuellos. Started soft for the Royals on the uh base rookie auto. You know when Dylan's doing everything. Jake Irvin Refractor. Yeah right. Dylan's got to let us know what's going on out there. I like it. I like it. I like it. Prism rookie is Caballero for the Mariners. Got Cardinals Jordan Walker. Francisco Alvarez Future Stars and Freddie Freeman All-Star Game Refractor. There's a Raleigh Green Refractor there on the debut rookie and Lava Lamp. This one's going to be Robbie Grossman to 175 or sorry 125 on the blue and green Lava Lamp. Action Stars is uh Goldschmidt have a Logan O'Hoppy prism debut rookie and Andrew Benintendi. So sounds like there's some like multiverse stuff going on. Everything got me multiverse. I don't know. I'm so confused. I'm always confused with this multiverse nonsense. There's a uh Refractor Jake Bird rookie. Adley Rushman insert. There's a Austin O'Reilly. Reese McGuire Refractor. All-Pros is Freddie Freeman. Titan's rookie got to be Jordan Walker for the Cardinals and Chris Morel rookie for the Cubs. There's a prism of Kyle Lewis. D-Bax. Sandy Alcantara. There's a All-Star Game rookie of Kodai Senka for the Mets. Rookie Randy Vasquez Yankees. There's a negative Matt Reynolds going to the Reds. Negative Parallel. Prism 1 Yepes. Cardinals. J-Rod Future Stars and Elvis Andrus on the back. Refractor. Alrighty there goes box one. Box number two. Come on debut. Let's do it. Oh geez Texas Stars with another kickin. Okay let's say. That's a bad sign. Oh boy. Ben says alien dance. I agree. Not sure what that means but I'm in. No I would not. No I would not. None of these are our cards so we will not be burning anything. Oh 100 percent. 100 percent Ben. I'm not burning anything. I'm not burning anything. Alrighty good luck to your guys box two. It can be anybody. The answer's still no. Targeting. How we have targeting on the first play of the half. Alright guys good luck on box two. There's a Ezekiel Tovar prism. Rookie debut. Kyle Lewis refractor. D-Bax. Got a Gunner Henderson insert for the Orioles. JP France. Got a Will Smith All-Star Game refractor. Dodges. Andrew Benintendi. Andres Jimenez. Titans as Aaron Judge. Refractor. Rookie. Levi Stout for the Reds and Gavin Stone. There's a prism rookie of Levi Stout. Brett Bady insert. Refractor is Jonah Heim. It's a Jake Alune Nationals rookie. And Purple is going to be Patrick Corbin to 250 for the Nationals. Nets. There's a Jazz Chisholm Action Stars. And Otto is going to be Cody Clements on the Purple Otto to 299 rookie for the Phillies. Purple Otto. Refractor rookie is Jose Caballero. Prism Brett Phillips. Luisa Rias. There's a Brenton Doyle refractor rookie. And that one's going to be the 199. A lava lamp of Brett Phillips. Former Ray. Go Rays. Ray's Legend actually. There's a Jared Kelnick prism. Brett Phillips. And Jose Barrero. Roffy Devers. Sonny Gray. Tate Oscar refractor. Michael Harris Action Stars rookie. Joey Vado and Gabriel Moreno. Box three. Good luck here, guys. Top Scrum update. This one is hobby. Six box case. Yeah, Toronto doesn't have the biggest checklist in this one for sure. There's game Moreno updates. They have Vladimir Guerrero Jr. autos. Not too much after that. There's Kevin Kearmeyer base. Not a ton for the Toronto in this one. For Moreno update color probably the most. And then those Vladdy All Star game autos would be our biggest hits. Good luck everybody. And we'll do a division's case next jumbo. Right? Good luck here, guys. There's a game Moreno rookie debut prism for the Blue Jays. That's the one we're talking about. There's a Josh Young Rangers rookie refractor. There's a Alexis Diaz for the Reds refractor. Dylan Tate. Future Stars. Bobby Witt. There's a Action Stars Vladdy. Titans Peter Lonzo. Got Corey Jokes refractor rookie for the Astros and Thor. There's a Jeter Downs. That one's going to be prism rookie. Garrett Cole insert. Fractor All Star game Mike Trout. Angels. Payton Battenfield refractor rookie. There's a Bobby Miller on the lava lamp to 2.99. Rookie Dodgers. Tatis Action Stars. Princeton Doyle. Anthony Volpe. And Otto is going to be Lyndon Sosa for the White Sox at 250. Rookie. Nice one there. White Sox on the auto. Got Jared Schuster refractor rookie. Prism debut Bobby Miller. JD Martinez. And a Rookie Kevin Kelly for the Blue or for the Rays. Rays. Negative Stewart Fairchild Reds. Brett Beatty. Future Stars or Action Stars rookie. Prism Nikki Lopez. One more handful in box three. Rookie Masatake Yoshida. That's for Red Sox. Insert. There's a Josh Young Rookie All Star game. Nick Ahmed refractor. Action Stars Riley Green. Tigers. And Oscar Colas. Debut on the back. Alrighty. Three down. Two or three to go. Three down. Three to go. Appreciate everybody grabbing spots on this one. We got one more break and then Sam will come in at five tonight. Have some more group breaks for sale. Check out the break schedule guys. It's linked in the chat. You can always see which breaks are going on and what time and what time. Thank you Josh for taking a couple more in inception. Appreciate you sir. Good luck here guys. Box four. Can't believe we missed M&M concert ma'am. Oh no. Can't believe we missed it. He's going to watch it later. Don't listen to him. Don't listen to his oh no. He's gonna watch it later. Five o'clock and eleven o'clock. Clock in. Watch it twice. Clocking in. Watch it twice. All right up to Florida State wins. Get an M&M concert. Come on dude. What's better than that? That's our half time show right there. I asked this question. Ireland got almost exclusively bulldogs but who we think's winning this Bama vs Georgia game. Probably the best game today. I would have to think. I mean I can't can't say for it before it starts but probably going to be the best game today. And I'm thinking Georgia. That's what everyone was saying earlier but there's a Riley Green for the Tigers. Joshua hopes Bama. Joshua and Carl. Joshua and Carl both said Bama. There's a Refractor Oscar Coloss. Dave Vue. Donnie. Donnie goes. I just seen her stars. I just seen a FedEx truck at my apartment complex and internally shouted out FedEx. FedEx. Action stars of time. I love that. There's a Brandon Williamson Refractor rookie. It's talking to yourself. It's a gunner. It's about right. Got Bama on the parlor. That's why I figured Joshua, I like it. I don't hate Bama winning today. I don't hate Bama winning today. Would make it interesting. They probably kicked Florida State out for Georgia though which is not gonna be happy. Prism, Jake Bird. They're fine with anybody though. We'll try Georgia would still stay in. Rookie Dylan Dodd. And blue is Ryan Yarborough to 150. Yarborough to 150. Got a gunner. Action stars. Prism Tommy Pham. And Joey Wendell. Pretty good bleach. Nothing crazy so far. Nothing crazy yet. Pretty solid overall. There's a Prism of Elvis Andrews, Max Scherzer. Say Aaron Judge, All-Star Game. You get a nice low number here. Somewhere in these next couple. There's a Joey Weimer debut. 299 is Christian Pasche. Prism Brandon Fott. And Matt Strom on the Refractor. Definitely need to see some low numbers here. Turn it up a little bit. Altuve Refractor. There's a Doliz Garcia All-Star Game. Joey Ortiz. Gonna be for the Orioles rookie debut. Action stars Acunia. Titans Vladdy Jr. And Otto is gonna be JP France on the Refractor out of 499. Astro. He goes Stroze. JP France starting pitcher Otto. There's a Kodai Senga debut rookie. And that'll do it for box number four. Oh no. Ollie Gordon's hurt. Oh no. It's not who you want hurt. Box five here. Good luck. Top's Chrome update series. We'll get the full case going next division. This one is hobby. We'll get divisions going next full case. Again we are fill up on the daytime. Do have breaks. Still spots to go with Sam and Jake tonight starting at five. Check out the break schedule guys. Fortnite event was crazy says Clubhouse. Really. That's what Dylan kind of said when he walked in. Portals going everywhere. Very stuffed. I have to see some nonsense. I like it. I like the nonsense. You like nonsense. And Sam has a dual case Bowman Chrome later today guys. Hobby and choice has Orioles, Royals, Angels, Brewers, Phillies, Mariners, Cardinals and Rangers left. Eight to go. Eight to go on Bowman Chrome, Hobby and Choice dual case. Those teams are on sale as well. Unfortunately. Yeah, but if we do win, we'll be undefeated. There's like nothing. And there's probably like 10 five star recruit or 10 five star guys on our team. So we should be able to sneak in maybe, but I don't know. I think Justin taking one of the dual case. We should be down to seven now. Yeah, I don't know. I don't know how they're gonna treat us here next week. I'm not sure. Yeah, divisions is next. Yes, it is sold out. We are going to get that going here in just a few minutes. I don't know how the how the committee is going to feel about us. I already don't love us. So even with Jordan, they weren't loving us. So not going to be surprised. Not going to be surprised if they kick us out. Not even a little bit. Hey, good luck, sir. There we go, please. Second break ever luck. Let's go. Appreciate you choosing us. All right, guys, box five. Wanda Franco, Jose Barrero, got a Rangers, Josh Young insert. Casey Schmidt, rookie for the Giants got Shohei on the all star game refractor. Say Gio Arcello refractor. Got Francisco Alvarez debut. Luba, Titans, Peter Lonzo. Refractor rookie debut is Michael Harris for the Braves. Last year's NL rookie of the year. Say Prism, Luis Arias got a Mike Trout insert. Boba Shet all star game. Say Edward Julian refractor rookie. Say Bryce Miller negative rookie. Cole Reagan's prism rookie. Matt Mervis. Yeah, that's, they will. They'll probably put two in if Bama wins. They'll probably put two in. You don't have to worry about an SCC team being in there. Jesse Winker on the prism. You don't have to worry at all. SCC team will be there. There's a Masatake Yoshida on the refractor rookie. There's a Yandy Diaz, Mitch Hanniger prism for Giants. Anthony Volpe rookie action stars. Yeah, don't got to sweat that one. This one is going to be for the Marlins on the rookie auto Xavier Edwards to 199. Love the Aqua shimmer. Nice looking card there for the Marlins. Almost a little color match. Aqua shimmer. There's a rookie debut of Shay Langlears. Prism Jake Irvin. There's Garrett Cole. Yeah, that's the that's the biggest worry as a Florida State fan is that Bama wins and they put them both in. Bama and Georgia. Fertigistars of Rutchman. Lorda Scurrio. Say one thing on the refractor. Yeah, I like those two. The Aquas. I love these. These right here. The lava lamps too. This one's a 299 Nolan Jones rookie for the Rockies. The lava lamp. That's one of the new design this year. I really like them. And Adley Rutchman debut on the back. All righty here, guys. Last box. Box number six. Top scrum update hobby. Guys, we got divisions filled up for the next one and we'll get it going right away. Good luck everybody. Last box here. Come on, debut patch. Well, they slowed down the scoring, so my under over a hundred is in danger. Good luck on this last box here, guys. We'll get Jumbo going next. Gikori and Russell taking spots for later. Appreciate y'all. Again, Sam does come in at five. Sam and Jake going to be ripping more group breaks tonight. Got some Star Wars baseball basketball and football. Got more personal tomorrow morning as well. We'll be back here on YouTube. We're doing personals all morning. Yeah, I just want to get some personals. They will be doing some tonight though. So if you order now, it'll probably rip tonight, but we'll have some tomorrow starting at 10 a.m. Yeah, but if they beat Georgia, they'll jump Texas. If they beat Georgia, absolutely, we'll jump Texas. Texas beat Bama when they were still figuring out that QB situation. I don't know why Milrow thinks he's the highest trophy winner. He was sitting on the bench when they were doing all that. Yeah, if Bama beats Georgia, they will pass Texas and us. They'll be probably two behind Michigan. There's a Bobby Miller debut refractor. I just think they give so much to Georgia being number one. I would think that they would give it to him. Maybe not. Maybe not though. Maybe that moves Texas up too, honestly, if Bama beats Georgia, which would suck. Aaron Judge. There's a Austin Hayes. There's a Tyler Alexander refractor. There's a Bobby Whitt. There's a Jeter Downs refractor rookie. It was good, man. It was good. That would have been interesting too if Oregon won. It would have been interesting to see what the committee thought about that too. So I'm thinking Florida State lucked out there again, so hopefully it keeps on working for us. We've got a radiating rookie coming. There's a Blake Perkins prison. We've got Anthony Volpe rookie. Kunia All-Star gang. Brent Hedrick refractor rookie. Our radiating rookie short print is going to be Yuri Perez. Nice one there, Marlins. On the radiating rookie short print. One per case, even less than that sometimes. It's Yuri. Action stars Adley. Wendy Peralta on the prison. Riley Green. Future stars. Yeah, no, I feel you bleach. It's more because of the, I guess, throughout the season more pictures get called up than bats, I would think. But yeah, I feel you on that. There's a Greyrod on the rookie. Greyrod rookie insert. Wander Franco All-Star game. There's a Tanner Baby debut rookie. Guardians. Peter Lonzo All-Star game. Titans J-Rod. And Otto. This one's going to be a Zach Thompson rookie Otto there for the Cardinals. Zach Thompson on the rookie Otto. Yeah, so a little less than a case for sure. Or a little more than a case. Blake Perkins refractor rookie. I think there's 24 packs, six boxes in a case. Not great at math, so we're probably one and two or three. Say, Ryan Feltner there to 399. Pink Yordon. Prism Hunter Brown. And Mason Miller refractor debut. This is a few more. Prism Mason Miller. Got Corbin Carroll. Rookie is Anthony Volpe Future Stars and a Spencer Strikeout. All-Star game insert. Greyrod on the refractor. And that'll do it. We'll do it for 2023 tops Chrome update. Well, it's hobby six box case number eight. Do a quick recap and then we're on to Jumbo. Murie Perez on the Marlins with the radiating rookies to 299 Joey Wendell. We had Brett Phillips to 175, had a 150 year over 199. We got a Robbie Grossman to 125. Zach Thompson Otto got Kwayas Otto 499 JP France to 199 Xavier Edwards 299 Clemens and a 250 linen Sosa on the autos. Alrighty guys, get that going or get that uploading and we'll get Jumbo going here.


Hello, all of you, I would like to welcome you all to today's class. We looked at in our last class some aspects of Peterson olefination after we had discussed the allyl and vinyl saline based chemistry. We saw very interestingly that if we have beta salinol then they can undergo syn elimination under basic conditions which is what is called as Peterson olefination. It is a very interesting reaction as an alternative to Wittig reaction and we discussed the mechanism of that where we saw a 4 member oxygen-silicon containing intermediate. And then of course as we saw that say for example this kind of beta salinol which is having a 3 O configuration can lead to the formation of the E isomer under basic conditions. And under acidic conditions it can undergo anti elimination to form the Z isomer and we discussed the mechanisms in detail. Then also we saw one cyclic case where cyclohexanol which is multiply substituted with various hydroxy groups and saline moiety that we saw how under different conditions the conformation allows the elimination of the beta salinol moieties to give the E or different types of regioisomers of the cyclohexane substituted molecules. Then we also saw the carbon an stability and why the carbon ions which are alpha to the silicon are more stable than normal carbon ions which do not have silicon moiety. And then finally we looked at the epoxidation of the vinyl salines and how these epoxides which are sensitive towards H+, that is the proton under water conditions can give to the ketone or aldehyde and under say HBr conditions also they can give the different types of double bonds depending on how the opening allows. If the opening of the epoxy salines are carried out to give beta salinols and if they are pursued in the same acidic medium then of course we get anti elimination similar to what we have discussed it here. And if they can be taken up separately after the beta salinol form then of course under basic conditions they give Z signal elimination to give this kind of E isomers. Now we will move into the final topic of our course and that is Simmons-Smith reaction and the Simmons-Smith reaction is a very interesting way of carbon-carbon bond forming reaction. It is called as an organic chelotropic reaction which is involving an organo zinc carbinoids. It is not a carbene but it is a carbinoid that reacts with an alkene forming a cyclopropane. What are chelotropic reactions? Chelotropic reactions are a subclass of cycloadditions in which on one of the reagents both the new bonds are being formed. That means if this is the reagent and then both new bonds are being formed on the same atom that is this alpha. This is how the reaction is termed or classified as a chelotropic reaction. So, if you have a double bond like this and suppose you have formation of molecule like this where you have a species which allows the incorporation of a single carbon. So, if you have something like this here with a carbene or carbinoid whatever you can take it then what you are doing it is that you are forming both the bonds like this here and that is what is called as a chelotropic reaction. So, a methylene or certain other simple alkylidine groups can be delivered to the alkene simultaneously forming a cyclopropane and this is what is a chelotropic reaction. The configuration of the double bond is preserved in many of these reactions and that is very important from the point of view of application in organic synthesis because the reaction is highly stereo specific. What we are talking about is the Simmons-Smith reaction and the originally developed procedure that employs the reaction of diiodomethane. So, you have diiodomethane is something like this here CH2 in the presence of zinc copper couple. So, you have a zinc copper couple which allows a finally divided or finally spread zinc species zinc atoms and they allow the formation of cyclopropane in the reaction with olefins. Now, this is what it is the zinc copper couple diiodomethane it is expected or believed to form an intermediate of this type which then interacts with the double bond. So, this is not a free carbene but it is a carbinoid type of intermediate zinc carbinoid and that the transition state that is proposed is like this where if this olefin reacts with the carbinoid here. So, there is a simultaneous bond formation between the carbon of this zinc intermediate with the double bond. Of course, you will have something like this and at the same time the carbon iodine bond is breaking the iodine and zinc bond is forming and the carbon zinc bond would also break at the same time later on to form the cyclopropane and of course, you get the zinc iodide. So, this here this CH2 part of the Simmons-Smith reagent gets transferred in this particular fashion. Now, this is also termed as butterfly transition state because it looks like a butterfly. It is known that ultrasonication improves the formation of these organo-zinc species and therefore, the reaction occurs faster and that suggests that the reaction occurs at the surface of the zinc. It is believed that when diodomethyl reacts with zinc it forms this species which can of course, be in equilibrium with another species and zinc iodide. So, it is expected or it is believed that either this or this or these are the species which are involved in the final cyclopropanation. Now, pure carbines are excluded and a metal carbinoid organo-zinc reagent is likely to be involved in the mechanism of such reactions because what has been found that these kinds of reagents react with allyl alcohols of this type where there is a specific stereochemistry of the OH group. For example, alpha then the cyclopropanation takes place from the same side on the of the OH group and suggesting that there is some sort of chelation. Not only allyl alcohol but even homonyl alcohol of this type where the hydroxy group is alpha and the geometry of the cyclopropanating also becomes alpha. That means there is some chelation that is involved with the species that is holding the zinc with it so that it has some Lewis acidic character. It is a very important reaction and a very useful method and it is generally preferred over other cyclopropanations. The only drawback about this reaction is that it diodomethane is somewhat expensive but then alternatives like dibromomethane or diosomethane and zinc iodide are also reported a combination of diosomethane and zinc iodide. But there are also have been other improvements. For example, furukawa has made a modification where diethyl zinc is used along with diodomethane and it is believed that species of this kind is formed along with the expected zinc carbinoid species like this and of course ethyl iodide is also expelled. And it is believed as I have mentioned earlier that these are in equilibrium with this so that we have the species of this kind as well as of this kind and of course we have zinc iodide all of these help in kind of chelation with the hydroxy or any oxygen or nitrogen this moieties which can then guide the stereochemistry of the cyclopropanes. The furukawa modification is very useful particularly when cyclopropanation is done of an enol ether and this has been utilized in the cyclopropanation of carbohydrates which are generally difficult to carry out. For example, if we take diodomethane here diodomethane and of course diethyl zinc we expect an intermediate of this kind to form and when the reaction is done this particular OR moiety which is oriented in a beta fashion allows the cyclopropanation to take place from the beta side. This has been published in 1995 this is the reference and of course these are the kind of transition states that are proposed here as you can see that oxygen of course will have a chelation with this. So in this particular chelation which is beta oriented allows the cyclopropane ring also to come from the beta side. So both of them are beta oriented and if we take an ester of this kind here as you can see if this ester group becomes beta then both the cyclopropanes are formed that is both double bonds are cyclopropanated from the same side as the ester because the ester oxygens first chelate with the zinc carbinoid species and give the cyclopropanated product in such a way that the two cyclopropanes come in the beta oriented. As you can see it is 80% and the other one is only 20%. So that means the steric hindrance does not play so much an important role as it is the chelation with the ester group that dominates. In a similar fashion even acetates have been found to give the cyclopropanation and the chelation as you can see is through the acetate oxygen to the zinc part of the zinc carbinoid and even open chain type of molecules also give if we have an asymmetric center like this in which OH group is beta oriented. If we orient the molecule in such a fashion as you can see the OH group is beta this is also beta so this is the ratio is 130 is to 1. So this has been published in 1995. So you can see that there is a huge effect of the chelation with the zinc carbinoids with the hetero atoms leading to the formation of the cyclopropanes. It is an interesting example where it has been found that even if the nitrogen is present that allows the cyclopropanation to take place in a very interesting fashion where for example if you would add diethyl zinc and dihydomethane then you get the cyclopropanation as expected from the same side as this. If this is beta then this is also beta. And of course as you can see the dastier selectivity is more than 98%. But it has been found that in case the reaction is put along with trifluoroacetic acid then what is found is that the geometry of the cyclopropane is opposite to the geometry of the carbon nitrogen bond. So here it is beta, here it is alpha. And again this the sterile selectivity or the dastier selectivity is very high. How it has been rationalized and this work has been published in 2007 in ChemCom. As you can see here that the NH box, what is NH box? NH box is nothing but say if you put a double bond here then you have here N, here NH and box is COO tertiary butyl. So this can be expected to be in this way. There is a kind of enolization or formation of an immunol and that oxygen then reacts with the zinc and forming this intermediate and of course then the geometry of this allows the cyclopropanation to form from the same side as beta. So if this is beta then this is beta and this is beta. But in this particular case when trifluoroacetic acid is added this is the intermediate that is formed. This is what reacts but before that this particular species reacts with this intermediate to form an intermediate of this kind here. Where now the BOC group, this is the BOC group that now is made in a large group having zinc species and trifluoroacetic species and therefore blocks the top phase for the cyclopropanation. So here the steric hindrance comes into the picture and therefore the olefin attacks from the alpha side. So this is the alpha side and this is the beta side. So beta side is blocked and therefore the reaction occurs from the alpha side. And in this case it was also found that two equivalents of the reagents are needed. If the two equivalents are not used the cyclopropanation does not take place. That means the first equivalent of the reagent makes the BOC group kind of a derivatized and make bulky and then blocks the beta phase and the second equivalent of the reagent then allows the cyclopropanation to take place from the lower side. Now allylic alcohols also can very easily be allowed to react in the presence of isolated double bond. As you can see this is the allylic alcohol and this is the isolated double bond. If we do not have a double bond that contains an allylic or if we do not have a substrate that contains an allylic alcohol moiety simple double bond is there then the cyclopropanation would occur in this fashion. Or if we have an allylic alcohol here and then simple cyclopropanation would give a cyclopropane. Suppose it is OH beta then it is beta. But in a substrate like this in which we have both allylic alcohol as well as an isolated double bond it is the chelation that allows the reaction of the specifically this double bond to form the cyclopropane in this way. Now it is found that if you add chirally ligand like this then of course we can also do the cyclopropanation in an enantiose selective fashion and the work has been published in this particular journal in 2003. So you can look at this particular reference to see how the reaction has been carried out. But the main point here is that the amide part of the reagent interacts with the zinc along with the OH group of the allylic alcohol and they form a transition state that allows the chirality of this particular chirally ligand to be transferred in such a fashion that you get 95% enantiose selectivity of the cyclopropanated product. Now we look at the uses of Siemens-Smith product. For example, if we look at the cyclopropanation of an enol ether of this type for example, if you carry out Siemens-Smith reaction then we can get a cyclopropane like this. And now if we treat with H3O+, to this cyclopropane which is called as oxycyclopropane because it is having a OR group. So when proton is added to it then this particular cyclopropane opens up and forms an intermediate of this type where positive charge in or and of course you get hydrogen here. And now this particular part of the oxonium ion gets hydrolyzed with water where the water attacks onto this intermediate to form hemiacetal and OR and here there will be methyl group and then this opens up and loses the ROH to form the corresponding minus ROH and you get the corresponding methyl ketone. Now if we have in an enol ether the hydroxy group which is having a particular orientation such as alpha hydroxy then of course cyclopropanation occurs from the alpha side and in the same concept if we allow the H3O+, to react with it then of course as you can see that you can open up and here you get the methyl group having the alpha orientation. So it is a very interesting way of introducing angular methyl group here. This is basically angular methyl group, angular methyl group and with a proper stereochemistry which is dictated by the stereochemistry of the hydroxy group in the vicinity. So this has been employed in various natural product synthesis for example this Valeranone Valeranone has been synthesized for example this Valeranone can be expected to come from this kind of enol ether. Since the geometry of the methyl group is alpha, therefore if this is alpha then of course we can expect the cyclopropane to form in the similar fashion as we have shown it here and then the methyl group at the junction would be then the alpha because the cyclopropanation would take place from the alpha side because this is alpha. So and this can be expected to come from this ketone where we can pay out the reduction of the ketone and then this can come from the corresponding caromentone. So where the geometry of this cyclopropane, this particular isopropyl group here is fixed. Now how it has been done? I would like to show the synthesis of it is that you start with plus caromentone and react it with this particular intermediate and the basic conditions. Then what happens is of course that it undergoes an elimination of this kind under basic conditions and then there is a, so this intermediate undergoes elimination to form this particular product here. So you have an elimination of proton not here, the elimination of the proton takes place here and methoxy group goes off. So base takes the OH- takes up the proton from here and once this is formed then of course you can write it in this way that you have here ketone and now what you have is O-methy. So negative charge here under basic condition will allow Michael addition to take place and this is what will happen that leads to the formation of this intermediate. Of course the serochemistry we are not right now worried about it and then of course we get this and then you will have the ketone as it is here, ketone here. Now the anion again will form at this center and then of course you will get cyclization that leads to the formation of eventually condensation takes place and you get the elimination and then you get the product being like this and then the reduction of this particular moiety here. So what is going to happen is that you are get, you are allowing the condensation to take place here like an aldol condensation and now the reduction of this ketone gives one of the products to be this where the hydroxy group is alpha oriented. Now if we do the cyclopropanation of this particular allylic alcohol then of course you get the cyclopropanation from the alpha side because this is alpha oriented. I suggest that the reduction of this particular species you can try and write down the confirmation of this enone and then see how the lithium aluminum hydride allows the reduction to take place to give you alpha hydroxy group. So we can discuss that when the question answers will be discussed. Now the cyclopropanation happens then of course you can oxidize it in this fashion and then you carry out the Wolf-Krishna reduction to remove this so the ketone goes away and now if we simply use methanol and SCL then of course this going to open and you get the methyl group in a similar fashion as we discussed earlier the opening would allow to open in this fashion with a proton being here and therefore you get eventually under the acidic water condition Valera enone. Now grandisol is a pheromone in is an insect sex attractant of the cotton ball we will and thus the name is derived from this particular grandis and this is an interesting molecule here as you can see and it actually spoils the cotton field and therefore there is a lot of interest in the synthesis of this molecule one of the synthesis that has been done is utilizing this cyclopropane based chemistry. So if we start with a molecule like this the cyclopropanation has been done using Siemens-Smith reaction now between these two olefins the this particular olefin is electron rich therefore the cyclopropanation is specifically occurs with this particular double bond and once this happens we treat this with HCl. So the protonation of the ketone occurs here and now what happens is this moves in here with the movement of the double bond and opening of the cyclopropane ring in this fashion so it gives 1, 2, 3, 4 member ring here and of course you have 1, 2, 3, 4 and 5 this 5 member ring is here. Now this is how the this particular cycloxycyclopropane have been utilized it now apart from the angular metal formation. Now between the two carbonyl groups this carbonyl is relatively less sterically hindered because here there are two methyl groups here. So if we do the formation of the thioacetyl then you can get specifically this of course you will get some mixtures and now this particular intermediate has been utilized it for the synthesis of this Grandissole which I would like to show you how it has been done. So once you get this particular intermediate here this intermediate then you can then as I discussed earlier that you can specifically prepare this thioacetyl here sterically less hindered then you do the raninical based reduction of the thioacetyl where the carbon-sulfur bond breaks and you get two hydrogens here. So basically it is an equivalent of full Krishna reduction in a different way. Now if we react it with hydroxyl amine hydrochloride then you get the corresponding oxyme and this oxyme can be reacted with parieterine sulfonic acid and in the presence of a base which is 2,6-Qtidine at 90 degrees then what happens is basically here you have nitrogen and it forms O-tosylate and then you have a methyl group here and then you have a hydrogen group here hydrogen atom then you have a methyl here. Now what can happen is that one of the hydrogens from here under the basic conditions is picked up by this base which is the Lutidine and then takes up the proton from here forming the anion and then what you have then there is a elimination of this type and that leads to the formation of the corresponding nitrile. So it forms a nitrile and of course you get the this double bond here once the double bond is done then you can reduce the nitrile to the corresponding CH2OH via aldehyde. We have discussed this reaction where the nitrile can be reacted with the dye ball and lead to the formation of the aldehyde and that can with the excess of dye ball can give the corresponding CH2OH. So this is how the reaction can be done or alternatively you can also react this aldehyde with lithium aluminum hydride instead of dye ball and that can lead to the formation of the corresponding CH2OH. This is what the work that has been published in 1978. So these are the applications of the Simmons-Smith reaction in organic synthesis as you can see that the Simmons-Smith reaction is a very important reaction even the chiral version of this has been introduced and therefore it is a very important carbon-carbon bond forming reaction. So we will stop it here today and we will see you in the next class till then you can go to these cyclopropanations and various kinds of silicon based chemistry that we have talked and then we will see what is now how we can solve various kinds of organic synthesis problems using various kinds of reactions that we have discussed in this course. Till then take care bye thank you see you next time.


Right, we're both recording so 10th of February. Is it the 10th? I'm looking at his birthday from Aquarius rising Africa birthday shawty Real friend. It's really interesting. So it was your birthday last Friday It's shawty's from a quest writing Africa today, and it's my friend my lovely lovely friend Susie who's The world expert on dragons. It's her birthday tomorrow. So happy birthday to you for tomorrow Susie Hello, we are her talk about dragons. She knows so she does a lot of gets a lot of messages from dragons So hope she doesn't mind me saying that I'm sure she doesn't so anyway before we get into a discussion today How are you doing? Good? I think I think we're all kind of I know we spoke for a long time yesterday Catherine offline I think I think we're all feeling The vibrational weirdness of the stat it feels staticky and I told you yesterday like you know my dog Ravi He was behaving very strange I think a lot of animals are behaving strange and when I lived in California in the background Fisters down there They've just got back from a very long walk because I've got a very busy afternoon and evening of recording So they've had their normal for that exhausted, but yeah, isn't it weird? There's a lot of it going on my horses have just been sort of Galloping across the field and things like that in quite kicking their head their legs up in glee actually, but yeah Yeah, interesting vibrations isn't it so much going on and so much Backwards forwards is it isn't it isn't it isn't it? How are you feeling in the headspace? How are you feeling in terms of where you're being drawn to put your focus price? I want to focus on What what it our own again? We kind of spoke about this before we started filming our every individual. I think the biggest I Guess deep programming we all have to do is allowing somebody to dictate stuff for us and understanding What manipulation really is and what free will really is which I know that we that's what we were going to talk about a little bit today is like Understanding where we have boundaries with other people when other people try to control our own choices in our own free will And that's something that each it's like that Michael Jackson song man in the mirror It's like you we all have to take accountability for our own actions to really move into a new a new world of more positive energy It starts with us individually taking accountability for how we do try to manipulate or how we do try to coerce somebody into like Giving up their free will in order to do what we want and in my opinion when we do stuff like that Whether we're conscious of it of subconscious or conscious of it It's because of our own fear of our own of our own fragile state and when we try to manipulate other people's free Well, it's because I think we're afraid of our of our own divinity in the fact that maybe the universe doesn't support us Like they support other people which is simply not true the universe supports every person And we have to have that respect for other people's lives, too. If that makes sense. I hope that makes sense Oh, it makes massive sense to me and it's so interesting because it's so we would like watch me talk about this We've got so such a list of topics we want to talk about One thing I've been noticing so much over the last sort of month or two And I know it can seem quite picky to people and it can be quite irritating when People sort of pay too much attention to language But we know that language is a spell and what I've been noticing a lot recently Is how many times whether it's people who are doing videos or whether it's people leaving the comments are Using language like we must or or you must or we have to or we need to so need must things when anyone's telling you what you need to do What you have to do what you must do However, trivial it might seem people might say oh, I just didn't think about my words But actually look at the Gemarche aside of things look at things There's a reason why we say these things why we write these things and there's an energy behind that isn't it? And that's almost like the subtler side of things of what you were just talking about It's coming through at so many different levels and we become so used to it that we don't need it We don't notice it, but I've noticed how many people are You know sending me stuff and things which I really appreciate but you need to do this You must do this you must contact this person. You must listen to this you have to do this And I'm like whoa hang on a minute Yeah, it's like that out one of my favorite Alan Watts quotes when somebody I think I've mentioned it before when you know This big question like what is life? Why are we alive? What's the point of life and he basically said the point of life is to be alive the only thing you need to do is live That's it and and yeah, I think that you know, I've been noticing lately too When people have a habit sometimes of stating their opinions as facts And that's trying to be better about that myself saying like in my opinion or I think this way saying that this is this is just my Perspective doesn't mean it's the truth or it has to be your perspective And I think that's something you and I both like Catherine is hearing other people's perspectives because when you hear other people's perspectives It shapes it either makes you Believe your own opinion more or it allows you to shift your opinion a little bit because opinions are always changing And I do think sometimes when people state their opinions as facts whether they're aware of it or not That also is a form of manipulation You know, and it's kind of like what we're seeing with the whole Circus happening around us at the moment won't say too much about it where there is a lot of propaganda and a lot of Manipulating facts in order to coerce people into doing things that they wouldn't do under clear clear headspace and You know, I just I think about people who do like to manipulate regardless of whether they're aware of it or not I just think like I would never want to have a life where the people in my life regardless of whether they were a spouse A partner or friends a lover or whatever were with me just because I had done something to coerce them Into being with me, you know, I would want my people around me to be with me because they like me, you know You know, and they feel safe with me, you know It's you know You never remember what people say to you But you always remember the way they make you feel and I remember my eighth grade teacher told us that I think it wasn't my Angela quote, but I don't remember but the whole my whole life I've been like I don't want people to feel like I'm tricking them or like I'm trying to get something from them You know, I want people in my life to want to be with me because or hang out with me or whatever You know because they actually like my company and I like theirs because when you're in that relaxed state of non manipulation Not trying to control each other's minds. That's when the vibration can raise because you're both respecting each other sovereignty And that's a true relationship, isn't it? And I think it's a really really important point that you've You've made them and there's with all the stuff that's going on one of the things that just hasn't sat with me This isn't an opinion in terms of people are doing things right or wrong, but he's just never sat right with me Is the fact let's take the black cats the white hats and let's simplify it and you know Well, they have to do this because they're playing again against the black cats therefore They have to play against their own game. Well, no, they don't so for example My daughter played brilliant black football this weekend and what you do is you look at your opposition And if they've got a certain play Then there's so many different strategies you can employ There's never just one strategy and if they've got a certain game of playing you want to disrupt their play You don't do that by playing the same game as them, right? And that might not be a very good analogy But you know the point is is people say well They have to do it because of this and it's the same thing as what we're talking about and do you know what? Throughout this whole thing and you know, I don't know if I'm right or not only time is going to tell But it just doesn't ring true for me. You don't You know we fire with fire. Yeah, there's so many different ways. There's never one It's never solution a or solution b There's a million other options in between and I think this thing about people stating their opinions as facts is Really really important because whoever's listening to whatever videos whatever information reading whatever books They are all just an opinion Science is just an opinion at that point of time and it's never a black or white right and normally in hindsight You get more information that might either back up that opinion or change it completely I think This is where you can see the people that are sort of talking about things in terms of just wanting to discuss it and Keep the debate and the open mind and look at the world through a new pair of eyes Against this is what's happening and that's the fact and it's like it's becoming More more obvious to me. I don't know if it's just because I'm shifting and I'm getting more aware of it But then you and I have both seemed to be noticing this a lot Yeah, well, it's interesting because I see people all the time I have said this I think on your show a couple of times now Catherine like I'm bored With the Matrix I'm bored with talking about the competition that happened in November of you know A couple years ago. I'm trying to be careful what I say I'm bored of that because I'm realizing now that that was just Static over here from what's really happening over here with the over here seems to be again in my opinion So much more exciting and I agree with you like and I think sometimes and I know I know there's this Weird perception. I think a lot of people have You know, especially when we're used to watching TV or seeing movies But in the YouTube world like we're Catherine you and I are just two girls like normal average Human beings that I need to open up a platform any information We have is just from our own research or our own conclusions And it's not doesn't necessarily mean that it's correct And when I started my channel and started researching more of these historical stuff I did it because I knew something was wrong and I wanted to review things and I wanted to see what other people had to say If I can do present the research Let me get the feedback of what you guys think about this because I don't know what the hell is going on And I want to hear what you have to say too, but when people come in and say this is what's happening This is what the white hats are doing. Well, first of all, let me just put this out there This might sound kind of catty, but if we can figure out what the white hats are doing, it's not great They're not that smart. I'm a little concerned, you know So I've accepted in my own path that That there are going to be things that we're not going to understand right now when people walk around and say This is for fact. What's happening that I tend to kind of back away from that because how do you know? Yeah, and and are you is that coming from an ego place or not? It's like and when we're saying I know when we talked last time and we were saying we're bored and Got a little bit of backlash for that But again, we are just two people having our coffee chat on camera and expressing opinions and going through the roller coaster Like everyone else and the thing is just because we've reached a stage where we're bored doesn't mean that we're Criticizing other people that are still in that fact finding so when I was a child and when I have my children And I was teaching them how to ride a bike When you learn to ride a bike a lot of children put stabilizers on To help them stop falling over and then as they get more confident you take the stabilizers off And then once you can ride a bike you don't ever go back to your stabilizers normally We've been we've gone through having our stabilizers on we've gone through taking the stabilizers off and falling over a few times And now we're to stage where we're on our journey We're riding our bikes more on our own and I think this is the thing is everyone is at a different stage I wouldn't expect a three-year-old to not have stabilizers on right? You've you're all on your own unique Stages of discovery and there's some bits why I need to put my stabilizers back on because there's some areas of this information That I'm going into now So you and I had a lovely chat with mark up with the other day and I have got which I've never really paid attention to before I've got really fascinated by The true history of how long have humans been around in different areas of the world How the world was formed now it's hysterical because my husband's really into geology archaeology things like that I never have before and now I'm really fascinated into it because I want to know why It's all been covered up same same that's all yes I'm not at all about it practical and Want to I am very much putting my stabilizers on them because I am starting right from the beginning on that because I have Very little knowledge about all this and it's exciting like as every time I go to the museum And you know when I took the kids to the museum things I used to think why are they not showing us real dinosaur things and I've had this question Not our dinosaurs real or not because we're told there are but why are we not showing the real evidence? This all seems a little bit Disney to me Now again that these are areas that I'm just starting to explore and I'm very much at the beginning And so I'm taking in lots of information for lots of different things and I'm not taking any of it as fact Right, I'm just feeling into it and thinking does that resonate with me or do I need to ask more questions there? Yeah, and that's just a stage the way I do it and just because that's the way you and I do it Doesn't mean it's the way other people need to do it, but everything that's coming to me I'm now Feeling into it not just Intellectualizing it and sort of thinking does they sit comfortably with me or not and if it's a not It's like, okay. I need to I'm really want to do more research on this, you know Even I mean then but I was using it for me And I will say all the stuff that I'm like say I'm bored of now I am bored of but that was where we started like that that's something at the beginning had to happen in order to nudge you to take a look at at the situation with a different perspective and I still have you know the only videos on my channel that have been taken down are the ones that YouTube took down I've left everything up on my channel as far as when I was talking about that stuff more and looking into that stuff more But but again something has happened and I think it started happening to me maybe six months ago And I've always had spiritual experiences. I know you have Catherine I've always known that you know That's what led me off to India was because I was having so many spiritual psychedelic experiences that I wanted to figure out What was going on but now at this point Through all this like nastiness of the matrix that got us to where to wake up You guys know what we're talking about Something kind of evolved out of that whereas like you said I started going Well, why are they doing this? Hmm? Why are they trying to fool us? What is it about us? That's so powerful That they would need to try to keep us down Why are they manipulating us and that has opened up a beautiful path a beautiful path Of who we potentially are in the true history of of our civilization as humans You know the fact I mean I was so ecstatic when I realized in my opinion from some research that the 12 tribes of Israel were Galactic It made sense And I was like oh my gosh. This is this is so exciting. So this junk DNA They say we have is actually going back to possibly our galactic roots And we have family that's not even here on this plane of existence because of that and like that whoa Like that's so exciting and that is where I am interested That that's that's why I'm bored with the matrix is I want us to figure out who we really are Because I think going back to what we started with the manipulation try to control people try to control their free will If you understand that there is something really special about you Then you also understand that there's something special about everybody around you too That same spark of life inside of you is in behind the eyes of your friends your animals the trees And so you start to respect people more because they're just as special and unique as you are and when you have that understanding You stop wanting to control other people you stop wanting because you understand that everybody here has a purpose And that's where I want to start looking at that. That's where I want to go now This earth like I had an awesome conversation with David Cohen yesterday who you introduced us to and he was talking about My god into talking about all these different, you know land masses where there as we talked about with Mark outward Where there's possibly giants and it's like well our earth is so magnificent and we don't even understand the half of it And that's where I feel like my maybe it's because we are getting closer to that flip that some of us feel the need to go to a more positive Place of growth, but yes people who are just now waking up They're gonna have to start from the beginning again And that's why I know I've left my videos off where I talked more about what was happening the 1% their religious practices will say You know, I've left that up because that it that that is a necessary stepping stone But at this point I want to shift forward. I want to figure out like I want to talk about dragons I want to talk about giants. I want to talk about the galactics because that is exciting to me And that's coming from a place of love for humanity And also, I think it's exactly that and you can see just by a body language And I encourage people to look at themselves and say what excites them and for some people It will be this finding out and exploring and going down the rabbit holes So I know when I first started watching fall of the cabal and and now you've got Nick Alvia's good line TV, which has got all this stuff collected in one place, which is absolutely wonderful And you've got all these amazing resources that have sprung up over the last few years to really help people on this journey And I I know when I started down that journey, I had that all about that was up.  Oh my goodness. And so it's recognizing in yourselves, isn't it? It's like where you are being really happy with that. And I think going back to the thing about the sort of manipulation and that we started off I think that's where you can see it's like any time someone tries to ridicule someone else for where they are on their own individual personal journey Then that sets alarm bells off for me because we've got no right to ridicule anyone else We've all been there got the t-shirt and as I said, there's some areas where I feel quite knowledgeable about now And there's other areas which I've got so little knowledge on completely And I think that's absolutely fine and it's fine for us to all be where we need to be but to recognize it And I was having a conversation with some family members last night about I'm so pleased because of the work I've done over the last sort of 10 15 years that I can recognize so quickly now Where I'm slipping into bad habits when I'm in the company of people that Don't make me feel good or don't bring out the best in me and all these things and and that's not blaming other people It's just now I've got to a stage where it doesn't mean I don't do these things or make mistakes But I can recognize it so much quicker and cause correct so much quicker and then it's not a big issue Yeah, it's like our friend tomorrow's my favorite mantra for us cancel cancel like we need to see those things and you you know We know our thoughts are powerful We know we just don't understand how I don't think we understand exactly how powerful our thoughts really are and when you feel that coming just cancel cancel cancel cancel and And yeah, and I would say too. I believe you know people who feel the need to control and manipulate I think that's coming from a place of fear within them again Their own insecurities and so and again, that's something that only each individual person Can work on themselves and so I would Suggest is just my suggestion that I'm including myself We'd be including that we all start just working on ourselves and try to like break the bondage That we try to put on other people or bind other people to us because of insecurities We may have because even it through manipulation those insecurities are not going to go anywhere They're not going to go anywhere until you work on that and I think going into a new tomorrow a new earth It's going to be required that we we have to start releasing our our our control of situations and just surrendering To to to divinity into the play. I promise you I promise you in my opinion.  You know as we said at the beginning. You don't have to do anything You are enough as you are And having that feedback I mean what I love about our relationship and some of our other friends we've got is we can have really good discussions about these things and I've got I was out for war with my lovely daughter who is amazing So wise to her age is unbelievable All the years I spent on coaching I should just talk to Lois But in all seriousness, we've noticed a huge shift over the last six months in our dogs Lola and Indian and Lola and Indy have got very special. They're just just a beautiful very special energy about them and There's so much more relaxed at the moment now They've always been relaxed in this situation, but sometimes out and about if they meet people with sticks or Lola sometimes with some other dogs and things and at the moment. She's just Transcended so much of that and a lot of it is because of me because of the work that I've been doing now I'm not taking credit for Lola, but I'm saying what she was doing is a lot of what she was doing is picking up My energy my fuzzy energy because if I'm out and I'm thinking about this and that and some of the things and interactions and conversations I'm having and not in my highest interest and then that of course affects how Confident she feels being with me and now because I'm sort of getting better and better and better at rest in this As I said other people are just really noticing of just how much more relaxed she is When we're out on awards and things because I'm not giving off that high static so to speak. Yeah Yeah, I was totally well That was funny I think I told you cat on a private call with with my my little boy because he I've always thought he was high anxiety Because he was a rescue and there were some abandonment issues.  He's fine. Yeah hit me so hard And and so I try to work on that with him like being cool calm and collected around him And I asked we started saying like yesterday He was he like went back into puppy phase where he was pulling the recycling out when a chew on everything But I think but it was like it wasn't like He I could tell he wasn't doing it because he was anxious about anything. There was like your your course. The horse is kicking There was like an excitement When I lived in California right after college Now everybody knows California has bad earthquakes here in Georgia There is a fault line sometimes we have a but you don't really feel them and I will tell you Knowing people who move to California as an adult people born in California. There's a huge difference for how they handle earthquakes people born there Sleep through them. Whereas I would freak out every time But the animals whenever an earthquake would come if there was a cat or they would they would tell you they could feel it coming But the earthquake was coming and I feel like that's what the animals are feeling now They're feeling the fact that we're about to move into a new a new timeline with a higher vibration And I think there's an excitement coming from them and what's so pure as I think as human beings going back to the manipulation We do carry a lot of like Unnecessary fear. Yeah, there's animals are able to surrender more to the vibration of divinity Yeah before shake it off.  Just like you did as a So so, you know, it was like he was excited about something was happening and I even told you so I was like I need to check this human rises like something is changing right now Yeah, we don't need to check that because I haven't checked that for a while please let us know what it's like everyone but It is great, isn't it? And I think that would be my message for Anyone that it resonates with is tomorrow's cancel cancel cancel cancel So just you know looking at what in your life. Do you want to cancel cancer? And if it's me, that's fine You know, but it is really really important What are you needing to and just because you need to cancel cancel something now? Doesn't mean that you won't want to go back to it in six months time I think that's a really important thing, isn't it? We're talking about right here right now What is serving you what isn't where do you as an individual need to be and the more we recognize that I really notice a difference in the more The more people are confident in that themselves the more they react to a love and heart center To other people that they're interacting with yeah, it's whatever I think you everybody needs to wake up in the morning and I've been doing this myself So because I've watched Taylor our friend Taylor moon do this and I love it is this for my highest good This is the highest good of the collective and And if somebody is if you're watching something on YouTube and they they're stating all these things happening And it's scaring you just remember that none of us really know what the hell is going on So it's just that person's opinion. So don't let it scare you It's just that person's opinion Yeah Fantastic. So talk of moving into the love to our operation We are just about to do a really lovely talk with Lucy Davis who is all about moving into the love vibration So you will see that up on both our channels later and I'm I'm in wonder today I really am in wonder nature's coming out and I'm loving the expiration. I'm loving the new awareness that I'm feeling about myself And I'm loving the impact that my animals are giving me really good feedback on what's working for me and what is it So that's really helpful. Oh Thanks, Bryce. It's always such fun We've I keep meaning to make myself a natural cup of coffee for this. I was really gorgeous organic coffee with much mushrooms in so We might actually have a proper coffee. I'll make a note the planer nation I Don't know where the time is going. I've said this before but it's absolutely flying but in a great way every day is just like Wonderful at the moment It's the best is yet to come the best is yet to come see you soon everyone. Thanks. Hope you enjoyed the coffee chat


Welcome back to the channel in this video I want to talk about where you could take your harvestable organs your illegal items to sell them without being caught or Anything of that nature. So I have just been on this random planet here, and I got myself some Illegal contraband. That's the foremost. Let's get rid of that health stuff. What's going on there? Hyperfermia. Let's cure that Let's go to aid Please let me find something really quickly for hyperfermia Do-do-do-do-do-do there we go that'll do Right, and then I go down to my MISC and we have harvested organs value of 13,500 you could tell that they're illegal items because we've got our little yellow symbol in the bottom right hand corner Whereas normal items don't have one and stolen items have red red icons So anything that's a yellow icon is an illegal contraband item that is going to get you a lot of credits when you sell it But it is also just something that can get you arrested and things like that I haven't actually been stopped yet because I've been very careful with my illegal items But you can just go and sell them in a place called wolf It's a solar system. So if we come all the way back out to the star map here You can see that this is where you start Alpha Centauri, correct And I am currently just over here checking some stuff out But up here to the right is wolf now wolf has a planet and a place called the den over here I've been here once before so you can jump to it The the system and then jump to the place called the den or just fly there if you wish which I'm gonna do right now and In this area, you're gonna find a tradesman that you can sell illegal stuff to which is Exactly what we need like it's it's the the perfect easy place to go to at the very start of the game where you won't get caught and and all of that kind of Fun stuff you can just sell your things. So we're gonna duck it and I'll show you exactly where the guy to sell to is Now every kind of vendor has a limit on the amount of credits that they have for you to sell things to them But if you wait 48 hours their inventory gets replenished and their credits get replenished So if you have more than one thing and the person cannot afford to buy them off you You just chill and wait and then and then you'll get You'll get more credits to spend so this guy here Marcel do this. I Can sell you this mate? All right, let's go down to miss now. He's got 11,000 credits. Hopefully he's got enough for me No, that's what I'm buying from him. I need to sell 1687 so if you had multiple of these, you know You can just keep rinsing him until he spent all of his credits and of course as well You could just sell normal items to him So this is some stuff that I picked up in the constellation armor room where I stole it without using a Picklock and you can see it's worth quite a lot 1,156 you get a pack with it to 1,456 and a space suit, which is 4,426 pretty beast armor from constellation But I could just get rid of it and sell it if I wish to To this guy because it's just right there to sell to when you're bringing your illegal stuff anyway If you do have a whole bunch of stuff and he runs out of credits All you do is go over here You sit out one of these chairs pick whichever one you fancy which one you'd like sit down and it'll give you the Little thing at the bottom saying wait Okay, cool.  So yeah, that is how you efficiently and effectively sell illegal items at the very start of the game now obviously later on in the game You're gonna be loading up your ship with loads of things that are Illegal but you'll have different mods and different parts of your ships that you can hide it in and you'll probably find that vendors with Way more credits and money and such things but right at the start of game If you need a quick burst of credits This is the place to do it and it's right close to the beginning planet too So I hope this helped if it did hit the like button all that good So thank you for watching. I've been easy now you guys have been awesome


Hey, do you like writing? Do you like graphic design? Do you like data analysis? And do you want to make a lot of money? Well, then starting an affiliate marketing business is a really good idea for you. And it's something that I did back a number of years ago when I got started and have made over $20 million in my time doing affiliate marketing. I'm going to go over the cost to starting an affiliate marketing business. I'm going to go over not just the costs in terms of money, but I'm going to go over the costs in terms of time in this video and walk you through exactly how much everything costs and how much time I would say everything would take if you're starting an affiliate marketing business the right way and want to make lots of money on autopilot. Like I was able to do years ago and still to this day I'm earning tens of thousands of dollars a month from. Let's go. Now the great thing about affiliate marketing is that you can start an affiliate marketing business for absolutely nothing. You don't need any money to get starting an affiliate marketing business. So literally everything I'm going to go over right here is 100% optional. But if you want to start an affiliate marketing business the right way, this is what I suggest you do. And yes, it does cost some money and yes, it takes time. But if you follow in my footsteps I've earned over $20 million at this point doing affiliate marketing and I've trained tens of thousands of affiliate marketers some of whom have become multi, multi, multi millionaires even one deca millionaire that has gone through my trainings. So I'm hoping that I have a right place to talk from. Now the first really important thing when you're starting an affiliate marketing business is having a domain name and hosting. Having a website or a domain is really important because you'll need that to get accepted to a lot of the different affiliate networks such as Amazon and Walmart and a lot of other affiliate networks out there that you might want to join. Now for $177 you can have a domain name and hosting so you can have your own website for a year at that amount of money. And if you want to use my favorite company that I use for domain names you can check out the link down in the description or in one of the pinned comments. It's JohnCristani.com forward slash top three which is my top companies for domain names. Now the importance of having a website is that you'll need a website to get accepted to many of the different affiliate networks out there that give you products or services that you can promote and earn commissions from. Now affiliate networks are typically free. 99% of them are 100% free and the paid ones aren't really worth joining but some affiliate networks require you to have a domain name. For example, Amazon is a huge affiliate network that pays out tons of money of commissions. Hundreds and hundreds of millions of dollars are paid out by Amazon to different affiliate partners but you need a domain name to be able to resell Amazon's products and earn commissions from them. The next thing you'll need is a website builder and the website builder I recommend is ClickFunnels. For three months, it'll cost you $291 and I figure three months is kind of a timeline that will give you enough time to get used to ClickFunnels or learn how to build websites on your own. Now at $97 a month, that'll cost you a cool $291 for three months while you're figuring out the ropes of either building websites yourself or making money. ClickFunnels is fantastic. I still use it to this day. You don't need to know any programming whatsoever. ClickFunnels does a lot of that work for you and they integrate with a lot of other websites. That's $291 right there. I recommend about $1,000 for advertising. The way I do affiliate marketing is I've never been one for patience and waiting a long time to get the ball rolling. I wanna earn money right now and the best way to get yourself out there, to get your websites out in front of people is by using advertising to fuel that. So that's why I recommend $1,000. Now you could go out about affiliate marketing other ways. I have a bunch of free training videos on affiliate marketing, which show you how you can grow an audience on Instagram, on YouTube, on other social media networks.   So like us.  But you might not wanna do that. You might not wanna be a social media person. You might not wanna put your face out there. You might be embarrassed. You might feel like social shame or what would my friends think? What would my family think? Which is why I always bought ads. I didn't want to put my face out on the internet, but in the last couple of years I have and I hope you enjoy. $1,188 for training and support. The way I learned was I joined a affiliate marketing kind of forum for $99 a month. And I was a member of that forum for actually for years, three or four years until I was able to really get my start and start earning money in affiliate marketing. That was a lot of money, but it was really good because the reason why I need community and support and training in any business is because you might come against roadblocks or obstacles. When you're starting a business, when you're becoming an entrepreneur, nothing is ever gonna be step by step by step 100% laid out for you because that's why it's a business, that's why you have unlimited income rather than a hourly salary. So you need to have some sort of support when you're going through affiliate marketing or any business, whether you're starting e-commerce or stock trading or real estate, you need that support network in place. So that's why training and support is an important line item many people forget about. But beyond just training and support, you're also going to want to invest in going to the number one conference that happens each year in affiliate marketing called Affiliate Summit West. The reason why you wanna actually go to a conference of what you're doing is because that's what normal people do. They go to conferences to learn about the business they're getting in. They meet in real life folks that are doing what they want to do in real life.  Again, as I said, you can start affiliate marketing for free just by watching my videos. But the real way I recommend it if you're getting started, do all of these things. All of these costs to start an affiliate marketing business added up equals $3,656. That is a very reasonable price and amount to start a business. The typical business costs about a quarter million dollars to start or somewhere in the range of 50,000 to a 250,000. That's what most franchises sell for. That's what most business startup costs go for.  Starting a normal business costs at least 10 times more than the amount right here.  So you need to take it seriously and $3,600 is a reasonable, cheap sum of money to start a real business that can earn you millions. The costs in terms of time are also steep when starting a business, but so are the costs of time when you're starting a relationship or if you're starting a new workout routine, you need to invest your time to get fit or to get in a happy relationship. Same thing with businesses. I recommend 120 hours of trial and error practicing doing affiliate marketing, meaning spending those ad dollars, joining affiliate networks, going through trainings 120 hours, actually doing the affiliate marketing ads, writing ads, researching ads, data analysis, looking at offers, talking to your affiliate managers. By the same note, I recommend almost an equal amount of time learning, skills that are going to help you in whatever type of affiliate marketing you're doing, whether you're promoting nutritional supplements that make people strong or give folks beautiful skin or help people lose weight, or if you're advertising or promoting mobile gaming apps to get people to download stuff or what have you, or if you're promoting software programs or services, whatever types of products or services you're promoting, anything around can be marketed as an affiliate nowadays. You'll need time learning skills. Now the skills I teach in my training programs and on this YouTube channel are copywriting, how to use ad networks and data analysis and many other things, video editing, photo editing, et cetera. Using software programs like TikTok ads or Snapchat ads, Instagram ads, Facebook ads, Google ads, YouTube ads, Propeller ads, pop-up ads, push notifications, all these different types of advertising out there. These are a lot of big terms. Take time to learn and they probably sound like Greek to you right now. But again, they have help desks, they have documentation, they have support areas, they have trainings of their own. You can go through all of those and learn and become a master at whatever area you are looking to advertise on. Maybe it's Instagram, maybe it's Pinterest. You can become a master just by experimenting and reading through all the information they have to offer. Now if I didn't scare you off with those huge money numbers or those 200 hours of amount of time that you need to invest in this business, if you really want a serious take at it, then great because there is an alternative to spending hundreds of hours and $4,000 just getting started with affiliate marketing. And that's my training course, the super affiliate system which thousands of folks have gone through now and some people have become millionaires. I've even had one student become a deca-millionaire who's made tens of millions of dollars and I've had many more students make hundreds and hundreds of thousands of dollars, tens of thousands or even just thousands of dollars going through my training program. It takes the time down to 25 hours for training and part of the course is trial and error. So going through and getting used to working with Instagram ads, Facebook ads, Google ads, YouTube ads and all the different ad networks is all inside the course. We also give you $1,200 of ad coupons and we show you how to get that money for free advertising and we get you a free domain name and lifetime hosting as a member of our program. So effectively what you're doing is you are getting rid of domain name and hosting. We also have a website builder. So we give you pre-done landing pages for the top affiliate offers on ClickBank right now. The top 50 ClickBank products we have landing pages already done for you so you don't need to pay that money to click funnels, domain name, hosting. You have $1,200 of ad coupons and you have your training and support. The only thing we don't give for free is a ticket to affiliate summit. Well, it's not my conference but it would be exciting to see you there as well. So we take that down and you don't have to pay $3,000. My course is $997. And you have lifetime access to all of these things and materials and we update it frequently. We take the time of practice way down. You're still gonna have to do your own trial and error like any business to really build your business up but we take this down at least a skill building down to 25 hours and we dramatically decrease the learning curve that it will take you to actually get started in this business. And once again, if you enjoy writing, if you enjoy graphic design, if you enjoy data analysis or photo or image editing, affiliate marketing is a really great business that you should look into and give yourself a shot at starting your own business and making real money because jobs and wages and salaries, they're going away folks. It's the world's moving away from that. That's not where the opportunity is. Everybody already knows that you already know that if you're here. So if you wanna check out the super affiliate system, there will be a link down in the description or in one of the pinned comments that will give you access to a free training session which will teach you more about what it is I do as an affiliate marketer, how I've been able to earn tens of millions of dollars and how my students have also been able to earn tens of millions of dollars from doing affiliate marketing and completely change their lives. So check it out, the link is in the description. It's JohnCristani.com forward slash goat and you can check out more information. If you enjoyed this video, if you loved it, hit the like button. If you wanna see more content on affiliate marketing and learn how you can really get started, make sure you subscribe to the channel and check out my homepage, my channel homepage which has a bunch of free traffic methods which show you how you can start affiliate marketing with zero money, zero training or skills or experience just starting from scratch. We have a lot of videos that show you that way but in all sincerity, this is what I recommend you do. This is how I recommend you start and really get yourself set up to earn millions of dollars like me and my students have. Thanks for watching, talk soon.


Just getting to talk to the guys. There's a bunch of NASCAR fans here. It's cool to see the relationship and the military and the army just talking different to guys about serving and doing different things. What their favorite thing is to do. So it's cool to just have conversations. I enjoy getting to experience what they do here at Fort Bragg. I think it's fun because you get to some of the same adrenaline-chasing moments as you get at the racetrack when you get in those vehicles. You get to go ride around and riding in a Blackhawk. Getting to fly around there and see how they operate. Got to fire a howitzer, pull the lollipops, which is what they called it on the howitzer. And that thing, it's a big boom. So that was fun. But to see a driver come out and go through the same thing and a paratrooper that may be 18, 20 years old, showing him how I'm an expert with this weapon system. I'm a professional. So maybe a simple task for a paratrooper and it's appreciated by somebody. It makes them realize, hey, what I do is special. The soldiers out here, the opportunity to be appreciated, it means a lot. There's nothing like the national anthem at Coke 600. It's just a patriotic day. And 600 miles to remember it's also, it's always really cool to see the impact it has on those families.


Welcome to ITU Telecom World 2019 here in Budapest, Hungary. We're very pleased to be joined in the studio by Jennifer Manners, who's Senior Vice President for Regulatory Affairs for EchoStar. Welcome to the studio. Thank you. Now, I wanted to start off by talking about innovating together, connectivity that matters is this event's theme. What is connectivity that matters, and why is it meaningful in your opinion? Oh, that's such a big question. But let me drill down a little bit. I think one of the exciting things about what's happening with 5G is the ability to bring such advance and such exciting communications globally. But one of the important pieces is to reach everyone everywhere. You're going to need multiple technologies. So what 5G will ultimately evolve into is a network of networks which will involve terrestrial technologies like, of course, terrestrial mobile broadband, fixed wireless services. You'll also see things like HAPS, high altitude platforms, and, of course, satellite, which is where I'm most interested. And really what you're starting to see is you've got an exciting world of space right now with many high-speed geostationary orbit satellites already up and more coming on board. But you've also got this exciting world of non-geos. And these non-geo-stationary satellites are going to complement what's being done by the geos and bring lower latency. You're going to have a world of high capacity, high-speed, ultra-reliable, some high latency and some low latency means of delivery, which really matters because 5G is going to have a range of communications. For instance, much of the IoT world is going to be latency-sensitive but isn't going to require a lot of bandwidth. And so you may come up with some sort of combination. And when you get service out to rural users, it's highly unlikely from a cost perspective and also in some cases a terrain perspective that you're going to have mobile services deployed on the terrestrial. So you're going to have to look to these non-terrestrial technologies like satellite. And the good news is the technology is there to meet the needs. And also getting more and more accessible in terms of cost. Yes, I think that's one of the exciting things that's going on is the satellite industry and the HABS industry are involved in 3GPP right now. And we're working towards standards for a 2021 release. So we'll be part of the 3GPP 5G infrastructure, which of course means lower cost to consumers. And we've got a, I mean, we're here at ITU telecom world. We've also got a conference coming up, the World Radio Communication Conference. I'm sure you will be heavily involved there. But I wanted to ask you a little bit on the site. You also co-chair of the network of women. Perhaps you could tell us a little bit about that. Have you got any activities planned around our next conference? So this has been a great opportunity for the past four years. I've been the co-chair of the network of women for the ITUR sector. I'm really focused on just a couple of handful of study groups, but we're expanding it for the World Radio Conference and we're hoping to have, or we're planning to have an event. And we're still working through the details, but it's really to bring together all the women. And one of our big goals with the network of women is to try and develop young leaders. We really think leadership is an important role, and we find that actually having some mentoring programs where we're able to work with other women to help them maneuver through the ITU process, because it can be so complex. Do you think women get put off by technology or do you think there's much more of an uptake and much more of an enthusiasm for technology nowadays?  I think it's been more the doors have been harder to get open. And that's actually our focus is, we have some really, really, and we have had for years, really, really smart, capable women who could serve as leaders. And it's really been, how do you get through the process at the ITU to achieve those leadership positions? And we have seen, Vena Roat, for instance, was a past chair of the World Radio Conference and we'd love to see another woman chair. We've had women who chaired, Audrey Allison chaired, one of the committees last, WRC. I'm hopeful that we'll have at least one woman this year. So I think part of it is to really create that framework and enable women to take those leadership roles. And finally, you're here at ITU Telecom World 2019. I wanted to ask you, what's the value for you of attending events such as this? So this is my first time here and I've had a spectacular time. What's been really helpful is the panels have been fascinating, really interesting, well put together. The panel is having so many senior level government folks who are sharing their thoughts as invaluable as well as thought leaders. And then having the ability to meet with individual countries is very excited to see when I walked around the exhibit floor how many countries are here. So you can actually go and spend some time and talk with folks. And then the government of Hungary has been a terrific host and had a terrific reception last night and really gave us a chance to network. Wonderful. Well, thank you very much for joining us in the studio, taking the time to be here. And we look forward to catching up with you again at WRC. Thank you. Thank you.


Vussi Kweyama was born in South Africa.  As a teenager, he had been in and out of prison more times than he could remember. After a local life skills course, he decided to change his life. Forever. Aged 24, Vussi started his first non-profit organization to help local kids reach their full potential. He then successfully completed his bachelors and with financial support of the Tilburg University Fund, he obtained his master's at Tilburg University. Today, Vussi is an inspirational speaker visiting prisons and thanks to his scholarship, he is advising governments on their criminal policies. You can help make a change like this. Donate now.


your video can get a surge of views just like what you see behind me in one of my videos yesterday this is exactly what happened i launched it and then hours later there was a new surge of views how did that happen well i used one tool from google called creator studio app it's an android and iphone app to give you real time statistics for your videos get it on your mobile phone it's not available on a website and you can look at hourly reports exactly as they happen there's no 301 club in the creator studio real time youtube views and you can see the effectiveness of the five things that i did to give that surge of views hours after one i posted on twitter i made an announcement i got a new video go watch it two i posted on facebook i didn't just post on my personal facebook i posted on my facebook page i posted in my facebook group if you don't have a group create one if you don't have a page create one they're two separate things and then post in your personal profile where it's just you as well do those three things on facebook then the third thing i did as i went to google plus and i commented on my own video i clicked the little share button and then the plus one and i typed in a new comment and that shared my post to all of my social google plus social followers that's three the fourth thing i did is i posted on linked in who of you has a linked in profile did you know just like facebook you can post updates and when you do it goes to all of your followers well on linkedin i have thousands of followers it's my professional network and every one of them get updated whenever i post a video on the george show do that too because it'll help you get more views if you don't have a linkedin profile get one linkedin is a professional tool just like facebook is for personal linkedin is for professional you should have one and add me george venus i'd be happy to connect with you on linkedin now what's the fifth thing what's the fifth website clout.com that's where you go to get all of your social networks connected together you get a cloud score and you can use clout to schedule posts to your different social networks and clout will reward you with points those points are an industry standard even on twitter.com you can see clout score is now published next to every single person i have a clout score of 61 what is your clout score tell me in the comments below and do the things that you need to to raise your clout score because that is what will help you get more views post on all these five different websites every single video that you upload and create hype if you remember dan keemstar created a video on his tip about how to get more views use hype i did that i followed his advice yesterday i created the video how to get more views as a teaser to this video and they're launched only hours apart because i wanted to create hype to get you excited to watch this video did it work tell me in the comments below do you do you use hype to get more views tell me in the comments below so we can all benefit from your experience and grow together as a family because this is freedom and this is the freedom family you are part of it i am part of it we're all part of it and we're all growing together so grow with us and click that play now button right there on the video bar to get started my name is george founder of freedom and you've been watching click the first video for a fireside chat with george where he shares our future and how he grew from 20 000 to 120 000 in just one month and click the second video to see how to monetize all of your videos with just a few clicks to enable all ad formats and monetize in all countries and we will grow together as a family because this is the freedom family you are part of it we are all part of it and we're all growing together so grow with us and partner with freedom that play now button right there on the video bar is all you need to click to get started your secrets if you really look at yourself you will be speechless what happened to being doctors and teachers what happened to being your brothers keeper now with