ac mae rwy'n meddwl bod nhw'n bobl yw ddiwedd yn adeiladol a'r ffordd i, sydd yn meddwl mae'n meddwl gynnwyr ar hyn. Fe ddim yn fawr, mae'n ddodd i fynd i allu ddodi, mae'n ddodi i'n ddodi, o 100%. Ond rhaid? Mae'r oeddoch ysbyt yn shooter ac ynser. Stewr na ddiwedd yn uned byddwch gyda fwy fyddio bwyd teimlo iddyn nhw, rwy'n meddwl bod nhw wedi'u lwyf yn y rhaid ychydig. It's what we need we have to try to be able to do and if we do that We are going to have those days that you are talking about if we come in here and we've got a cobb on for something or whatever we don't do our best work we don't enjoy that day or whatever wherever you go and if you're going outwith your miserable something's annoyed you it takes the shine off things you go to Everton critically before you've even gone in yn. Straight away, you're waiting for the first misplaced pass, or you're waiting for the goal to go in, and you're waiting for the solution. You can go, what, I'm told you blah blah blah. Whereas if you go going, you know what, it's all right mate, it's not going to go. I can see you worried.  I think when you're up up, every player, he buys the best that anyone's ever seen. Every kid, they have the best, their fans are the best, no one understands it. We give them stick and go, you wolves know. But at the end of the day, who's having the best of time? Us going, ah, you know beds, you lot of them, experiencing it. Now, there's a lot of fun. I think, I'm sure you'll agree with me, whenever we've had that feeling that we're all together. Everton have been better. Moise worked really hard to create that. He was great at it. Do you know what I mean? Listen, he didn't, ultimately he didn't do probably what he should have done Moise. He should have won a trophy for Everton. We lost that, you know, we lost it at Wembley in the FA Cup final. We lost it in the semi-final against them when they were terrible. They were in his greatest days. But he got us fourth and he got us fifth. And I enjoyed a lot of good football under Moise. There was times when it was hard, but there was some brilliant days now. But you're absolutely right of what you've just said then about how you approach the game as a whole. If you, if you go and you're in a positive mindset and it doesn't matter who it is and you go there, if you're in a positive mindset from the start, then the atmosphere, the gown's going to be better. It's going to generate a better atmosphere. People are going to be singing. People feed off it. They're going to be singing. They're going to be happy and then that. You know what? You're absolutely right. And I know this, this whole, this whole, people have different interpretations about this and they'll say we're wrong. But you're absolutely right of deliverable thing about generating the atmosphere outside the ground. No matter what anyone thinks, right, whether people look like knobheads or whatever with waiting for a bus, right, with flares and all that, it doesn't matter, right. Because what they're doing is they're generating an atmosphere where they're all one, they're all together. Now the Man City thing pushed it over the edge of the bottle and stuff, but that was only, that was a few knobheads, right. But in a whole, they are saying to the, they're saying to fans, their own fans and their own team, this is who we are. And then they're pushing it to other fans going this is what we do, right. You don't do that. We do that. We give everything for our own team. We get, so that when everyone goes in, into the ground, everyone's buzzing. If they go in a pub, whatever, they're buzzing, right. Everyone's on a high. So when those players come out, those players, first of all, are thinking, we've got these with us, right. And the fans are up for it from the start. And everyone is in the same place. I've experienced this before and ever. And again, some people won't, won't, won't agree with me on this. But I remember going on a march before a game and being part of that march. And I remember the atmosphere outside. All the people who were marching outside were, had the same feeling, right. Now there was people who stood by and watched it.  And some people were like, I agree with what you're saying, but I don't necessarily want a march. It is the way it is. It is. But I remember going into that ground and carrying that with us into the ground. And the atmosphere was brilliant. And then we played the villa. And the atmosphere was brilliant because everyone who'd been there was like, it got them going. It was almost like, no, it was like a warm-up. It was almost like we were doing our stretches before we were going. Everyone was like, yeah, let's do this now.  You're waiting for something to happen, whether to be good or bad, rather than participating in it.


The Mindshare Committee in Fedora is one of the major leadership bodies in the Fedora community. And the Mindshare Committee also has the delegation around how a lot of our event and swag budget gets spent in the project community. So there is a group of folks who some are elected, some are appointed from different teams to the Mindshare Committee. And as a whole those folks help be the interface to the community for things like event sponsorship or travel support for a speaker or getting new swag ordered, doing a Lyme survey for a community survey.


dedicated to the strength of the nation proudly we hail yes proudly we hail starring Ruth Hussie in design for loving the United States Army and United States Air Force presentation now here is our producer the well-known Hollywood showman CP McGregor thank you thank you and greetings from Hollywood ladies and gentlemen welcome to your theater of stars where each week the brightest stars from Hollywood's world of motion pictures join us for your entertainment in plays we know you'll enjoy Ruth Hussie is our star and the title of our play design for loving we'll have the curtain for act one of our romantic story designed for loving in just a moment but first here's Wendell Niles who speaks for our government uniform of United States whether it is worn by a soldier or an airman means many things to many people to people abroad it means that the man wearing that uniform is a protector of the free way of life to Americans it means that man inside the Army or Air Force uniform is a defender of freedom and an honored citizen in an honored position to the man himself uniform means service to his country and a valuable career a career of personal satisfaction and development now once again our producer it's curtain time and here's act one of design for loving starring Ruth Hussie as Ruth Hardesty Ruth Hardesty look quite lovely there in that swank built more floral shop in Beverly Hills yes despite a rather hard look she was lovely almost as lovely as the flowers she sold on a certain Friday evening not so long ago about ten minutes before her quitting time one might have detected several things about her the disappearance of that harrod look a quick sigh a feminine motion toward a wisp of hair anticipation and as to the cause of all these reactions I could see him approaching the door he had come last week on Friday too he was so tall he almost had to stoop to get through the door and so good looking I tried to appear busy when he walked up to the counter oh good evening good evening I wonder if you'd show me some yellow roses weren't they well you you remembered yes I've always adored yellow roses yes they were so beautiful last week I decided to come back I'm glad I mean we're glad I have these yellow roses this week will they be all right they'll be perfect you want them sent to the same place yes Mrs. Vincent Charles 23-pound drive Beverly Hills Mrs. Vincent Charles 23-pound drive Beverly Hills oh and yes I guess that'll be all put this card in please I will thank you good night good night good night I watched him walk out of the door and then I looked at the tiny envelope in my hand I suppose I shouldn't have looked inside but I had to know who he was and who she was I opened the card he was Mr. Vincent Charles engraved and he'd written on it to my dearest one come through Tom I guess they say unlucky happening unlucky me I was still standing at the door when Madge walked over she was my roommate worked at the store well what are you gonna stoop about him who the one who was just in here oh you mean told I can Gary Cooper what a guy every Friday night he sends a yellow roses oh ain't that something and when I think of that unromantic droop I married Herman oh don't mention his name to me that's exactly why he's running that garage over in a soosa by himself no yellow roses yellow roses listen I couldn't get a sprig of parsley out of that character oh oh let's just forget Herman gee he was so attractive a nice name too Vincent oh well that's the only way to look at it dear I suppose whoops hold still a minute what wait oh I got it a gray hair don't do that to me that's the third gray hair somebody has found this week where's that delivery boy he could be anywhere oh it's you grandma yes it's me and don't be so smart okay grandma you heard me be sure to take these roses on your next delivery in Beverly Hills okay thoughts oh what don't let it get you down what that middle-aged spread you get out of here I'd crown him oh and if I can be of any further help kindly call my secretary now try to arrange in a point oh that little limp oh come on it's 25 to 6 let's go home imagine I had an apartment off Wilshire Boulevard near the brayer we had a view on one side but that was being cut off by a huge sign they were erecting we had dinner and wash the dishes and then I collapsed in a chair and Madge brought up the mail they sure are and ruining our view oh what a shame we won't even be able to see the vibrea tar pits mail not much only this brochure on Snow Valley nice place nice place for long underwear anything else college alumni news yours thanks class of 1941 used to be on the first page now we're on page four we're moving back into the dark ages dark ages oh now Ruth don't let it get you down seriously though March do you think I'm getting old are you kidding what really does it does it look like I'm getting a middle-aged spread oh honey are you gonna listen to what some little punk says no tell me Madge tell me the truth oh I'm telling you please after all you're my best friend well honey we all have to get a little older the way time has measured honey ask me I knew you'd been keeping something from me oh now Ruth please don't lose yourself you don't know how it is 27 going on 28 and having trouble convincing people you're 23 going on 24 honey I was there so long ago it scares me come on I'm sorry that's better blow it mother's hand I'll listen Ruth what's wrong with you you've been mooning around ever since that guy walked in the shop a week ago well it's very simple I want a man I want to get married that does it what every girl I ever knew cries her eyes out breaks her heart over a simple little easy thing like getting a man well that's easy enough for you to say you've got yours listen I didn't marry a man I married a carburetor that's why I'm here and he's in that garage in a Sousa well if I were you I'd go right back to him and drink crank cases the rest of my life not while I'm a sane person but mad oh well Herman was sort of cute whenever I was around him too much I wanted to hit him with a tire iron and you don't know what you've got that's all oh I don't huh I married an unsanimental grease monkey oh seriously honey don't let a little thing like the absence of a man in your life get you down a man's easier to land than a barracuda anytime you think so I've got a foolproof formula you do positively first of all you've got to clear your mind sweep out the cobwebs get your mind off getting a man but how can I do that easiest thing in the world buy clothes and go somewhere but where why not snow valley see I'd never worn a ski out all you'd look darling and you have your bonus well they wouldn't miss me at the store for a few days of course not that settles that you're going to snow valley all right and listen honey I've heard there are more men up there than pine trees really happy hunting grounds now the second part of my formula and this is very important you start now you've got to think of your perfect man then you'll appear hmm but how will I know oh you'll know you'll have a feeling down your spine like someone pressed a coat teaspoon against it did you use this formula to get Herman I was perfecting it at the time you see how far I had to go come on let's get you on your way up to snow valley I got my ski clothes around clip bus ticket which included my hotel room oh it was wonderful leaving the town and the apartment with the signboard that was spoiling our view of the tarpets all the way up to snow valley I did what match said I thought of my perfect man and believe it or not mages formula was working with that afternoon in the hotel lobby a little my man with a mustache walked up oh excuse me aren't you Ruth Hardesty yes and you arrived I just arrived this morning a joy to have you I'm Spencer Gaines the social director for the hotel how nice now there's a gentleman here who is a well to put it mildly anxious to meet you well his name is J. Frederick Klugell horn Klugell horn yes he's a gentleman right down there in the beige ear muffs oh a very old Texas family extremely wealthy well Miss Hardesty why uh why not as we walked over toward him I had that feeling match described a cold teaspoon on my spine no no it was a tablespoon I rolled the name over in my mind Ruth Klugell horn something musical about the sound as we approached him I could see Frederick had a high for it as a matter of fact he had a widow's peak in reverse back at the crown of his head kind of cute though and then we were being introduced and Mr. Klugell horn this is Miss Hardesty howdy Miss Hardesty how do you do Mr. Klugell horn you well I leave you two alone well Miss Hardesty I can't tell you how glad I am to meet you how nice of you to say so you came up here a week ago didn't know a soul that's a shame been sitting around here all week twiddling my ear muffs lonely as man from Dallas you ever saw did I seen you then I brightened up like a steering clover well you wouldn't give me the credit for all that most certainly work and Miss Hardesty I'd be most grateful if you'd have dinner with me tonight well I I think that would be lovely Mr. Klugell horn you mad mad person just call me Fred alright Fred and you know I think it's just fascinating the way you say you have more oil wells on your property in Texas than trees I'm loaded with them honey loaded but tell me why did you want to meet me well I'll tell you I saw you coming in you look lonesome girl I did and you look scared like you needed something protection care like you needed a man's arm around you oh Mr. Klugell horn Fred Fred besides that you're the spittin image of my daughter Amy she's about your age too 31 going on 32 imagine that he was a father and he thought I was 31 going on 32 I was never so embarrassed I excused myself ran upstairs and threw my things into my bag then I took the next bus back to Los Angeles mad was at the apartment when I returned honey you're back already you're back you I could swat you with this ski pole what's wrong oh you and your formula didn't it work your formula got me a Methuselah with a southern accent what did say what's that keeps blinking on and off a sign they finished it lovely lovely neon this I want to see oh no old maid starch stiff as an old maid smile oh no match no we pause briefly from our story designed for loving starring Ruth Hussie to bring you an important message from our government this is the air age we're living in and the young men with wings are the young men with a sure secure future you can be a young man with wings if you're one of the best because only the best can become aviation cadets United States Air Force will sign you up for aviation cadet pilot training if you pass the physical examination and fulfill two simple qualifications you must be between 20 and 26 and one half years of age and you must have at least two years of college or be able to pass an equivalent examination the finest aviation training in the world will be yours after a year of training and successful completion of the course you'll be commissioned an officer in the Air Force Reserve those silver wings will be yours outstanding graduates receive regular commissions in United States Air Force immediately ask for your application at your nearest Air Force base or United States Army and United States Air Force recruiting station and remember only the best are aviation cadets our curtain rises on act 2 of design for loving starring Ruth Hussie as Ruth Hardesty well right about here a little music is quite appropriate maestro a few strains of mood music for our lovely young lady of the Biltmore florist and Beverly Hills Ruth Hardesty whose excursion to snow valley ended in romantic disaster not to mention the sign that greeted me from my apartment window old maids starch I went back to work at the shop in Beverly Hills mr. Graham Dible the owner was wonderful just asked me if I brought back any icicles I was a pretty sad character and not helping matters out in the least he had to come in Vincent well good afternoon good afternoon you seem surprised I am why this is Tuesday you usually come in on Friday a birthday are you want yellow roses two dozen this time I think very well send them to Mrs. Vincent Charles I can remember the name well and the yes and the address very good and one other thing yes well you were you sure that you have the address a 23-pound drive Beverly Hills that's right I thought it was and you'll charge it yes I will well I I guess I'll be moving along good night oh no not that door that leads to the right on a box of cardinas well I'll be going hey I can't see of course not you put that flower pot on your head instead of your hat oh good night good night there was something strange about mr. Vincent Charles somehow I thought I saw a glimmer of something in his eyes oh but how ridiculous of me how can I deny those of Mrs. Vincent Charles I want to know I dashed back to Sammy the delivery boy he was loading the truck Sammy Sammy oh hi it's where's the fire I wanted to be sure to get some roses on this delivery Mrs. Vincent Charles and Beverly Hills that name again you've seen her no but I remember the name I go to that place every week Sammy huh when you deliver the flowers this time we didn't see what she's like will you why well I want to know okay to its for you all do it well Ruth your private eye is here to report did you see her I saw and converse with the lady well so you what do I get for all the sleuthing oh now don't be difficult Sammy a lot of my own good heart anyway I'll tell you yes Sammy yeah see why are you so interesting oh Sammy will you please tell me all right I'll tell you I have never seen a more gorgeous thing did you say gorgeous oh what hair flaxen gold what eyes turquoise blue what a smile oh it would melt some end honest I've seen dames haha not like this one it's what he would choose he who oh never mind Sammy thanks thank you Sammy the trip home on a very a bus that night was a dismal one even the tar pits were shrouded in fog and when I got to the apartment I had another surprise waiting for me it had been magic day often when I got there she was packing I'm so glad to see you manage what in the world are you doing I'm packing honey well I can see that but why I'm going back to her roof back to Herman asuza oh madge oh I'm so glad he did the sweetest thing the sweetest thing you can imagine save but what in the world is this that's it he sent it to me oh looks something like an ashtray that's what it is honey Herm went out had a gold plate and everything well that was nice of him the sweetest thing oh what is it the hubcap off the 1928 hot mobility proposed to me and no wasn't that sweet and he put a note in it he did he always had a gift for words here here look lest we forget well wasn't that sweet oh I'm going to him Ruth and I'm never gonna throw another tire and I'll add him again not as long as I live oh good for you madge well I I think I've got everything all except my ashtray oh and Ruthie I'll still share your rent till you get another girl thanks madge is Herman gonna pick you up here oh no no I'll grab a cab I'm gonna meet him at a piston ring place on Main Street oh well honey you come and see us in a suit so won't you yeah I will madge you've been a swell roomie oh now madge please don't you won't be lonely now will you no madge I won't be lonely I won't be honest goodbye goodbye me miss Hardesty who Vincent Charles miss Hardesty oh dear oh come in mr. Charles thank you what oh you've been crying I just saw a friend off for Europe or somewhere in that vicinity you know how it is seeing old friends off yes of course but what are you doing here mr. Charles well miss Hardesty for over a month now I've been trying to get up courage to ask you to go to dinner with me well I just now accomplished that feat and I didn't want to wait until the store open tomorrow but mr.   Charles Chris I couldn't possibly presume you'd be free tonight mr. Charles fate must have directed you this is the first evening in months for which I've made no plans oh that then would you join me please why not beautifully you look even lovely at tonight the first time I saw you I've been meaning to ask you what brought you into the store well you see I'm an outdoor advertising man I make signs I made the one outside your apartment old maid starch yes I mustn't let my sister see it oh no no it's a lovely sign though you think so oh marvelous marvelous addition to the tar pit thank you you see I was working on that project and I happen to see you leave the apartment believe it or not I followed you to work I must confess I haven't been able to get you out of my mind ever since oh Vincent would you like to dance oh let's do you know something I have a friend who says when you really fall in love you'll know it because you feel like someone pressed a cold teaspoon against your spine only it's more like a cold gravy ladle only close Vincent close the curtain falls in the final act the design for loving our star Ruth Hussie returned for a curtain call after this timely message from Wendell Niles late last year the Congress of the United States authorized changes in the medical Department of the United States Army it's not the medical department of World War two not anymore today in addition to doctors dentists nurses and veterinarians there are 18 other fields for trained specialists in commissioned grade with all the opportunities available for careers career guidance and a safe secure future in the United States Army if you qualify you can be commissioned in grades from second lieutenants to colonel some of the medical specialists needed at this time are qualified clinical psychologists biochemists and especially pharmacists but the opportunities do not stop with these few categories 18 fields are wide open to qualified professionals in medicine and the allied sciences be sure to write for further information to the chief procurement branch personnel division office of the surgeon general department of the army the Pentagon Washington DC and I'll back at the microphone our star Ruth Hussie and our producer Ruth this is a very auspicious event on proudly we hail it's your third visit with us CP I'm always happy to appear on your fine program I think you'd be interested to know that I had lunch today with mr. Jordan oh I remember him he was connected with the very first US Army show that's right warriors of peace he wanted to see you again because you were so charming and you were the very first star to appear for free on any army show well that was nice of him and speaking of shows did my husband tell you what happened at our house during the last play I did with you know but your husband Bob Blum necker and I were on the phone this morning he said you'd have to tell the story well I was in the east when the show was broadcast out here and Bob had a dinner engagement with McDonald carry and late as usual was rushing to get dressed yes and little Robbie said daddy tell me a story the usual request well just then the telephone rang and someone said Bob Ruth's son proudly we hail we better tune in right away so Bob said to Robbie mommy's on the air you listen and she'll tell you a story then Bob went on with his dressing until he heard Robbie crying daddy mommy's going to let the people take me to an orphan's home you remember the story yes the family had adopted a baby boy because it looked as though they couldn't support him the court was going to return the child to the orphans home that's it well Bob finally convinced him it was just a story and nothing like that was going to happen to him and then he went back to his room to finish dressing and Robbie began crying his eyes out again again this time it was because I said goodbye CP and didn't say goodbye to either Robbie or Johnny well we'll have to set that right right now but first I want to tell you about our story for next week yes who's going to be with you next week Ruth and ladies and gentlemen our star will be the sensational young actress Arlene doll and a title of our bright western comedy deep in the heart this is the story of a girl who left Texas to bring her great talent for acting to Hollywood that's fine we'll all be listening and now goodbye Johnny goodbye Robbie and goodbye CP goodbye we should have done this next week ladies and gentlemen when we bring you Arlene doll in deep in the heart until then thanks for listening and cheerio from Hollywood Ruth house he appeared to the courtesy of the Hollywood Coordinating Committee which arranges for the appearance of all stars on this program script is by Rich Hall with music under the direction of Eddie Scrivenin this program is transcribed in Hollywood for release at this time Wendell Niles speaking


Hello, welcome to today's lecture. I hope you had the opportunity to go through the notes of the last class. What we discussed was essentially the mechanism of the McMurray coupling. How McMurray coupling can allow direct formation of the olefins from the ketones in an intermolecular as well as intermolecular fashion, forming different kinds of cyclic systems or acyclic systems. But since the formation of the acyclic molecules did not have a control over stereochemistry, we considered several possibilities of the mechanism and we ruled out the two possibilities in which the hydroxy groups could be attached to one titanium or two different titanium these atoms. And of course, then we settled for the mechanism in which the coordination or the kind of attachment to the titanium zero surface allows the reaction to proceed. The conditions we discussed also where we can straight away stop the reaction after the coupling up to the diol stage. And we also can allow this diol under the same conditions in a reflexing way to form the corresponding olefin. This also can be done both in an intermolecular as well as intermolecular fashion. So these detailed titanium zero base McMurray coupling we had discussed mechanistically and also saw the synthesis of humilene, which is relatively difficult to do under normal conditions, but this one step procedure allows the formation of medium size ring also. Of course, we discussed that disadvantages also that these conditions do not allow many other functional groups to be tolerated, but then there are advantages of getting such a coupling in one step. Then we discussed the reduction of alphabeta unsaturated systems, especially the bicyclic enone systems where the hydrogen or the electrophile attaches at the junction. And obviously, we came out with a discussion in which the incoming electrophile attaches always from the axial side and not from the equatorial side. There were again three possibilities that we considered. The three types of conformations cis-decaline having two different types of possibilities and trans-decaline having one possibility. And we ruled out based on steric factors as well as stereoelectronic factors and settle for the formation of a product like this, which is very useful in the steroidal systems or interpenoid systems based on the predictions or the rule devised by Gilbert's talk. Now we look at new reducing agents, which is a basically a silane-based reducing agent. So, as we can see that there are many commonly used reducing agents are reactive complex metal hydrides that are soluble in organic solvents. So, likewise example sodium borohydride or lithium aluminum hydride or di-ball or likewise similar the agents having different organically ligands on the hydride carrier atom are also commonly used. We have discussed all these earlier cases. For example, if we take in the case of lithium aluminum hydride we can have the OR here and we can have a reagent of this type where we increase the bulk and also the hydrophobicity. So, these type of various molecules are soluble in organic solvents in or at least partially soluble in organic solvents and the reductions can carried out. Simple hydrides such as lithium hydride or sodium hydride and potassium hydride are not good reducing agents as they are not really soluble in organic solvents. Of course, they react violently with protic solvents and obviously do not dissolve in other solvents such as ether or tetrahydrofuran. However, because they are ionic and they are kind of hard anions they behave as strong bases. So, these are used as strong bases to remove an acetic proton to generate anion. So, in this respect we have to see other possibilities of developing reducing agents and in that respect these silanes behave as a good reducing agents. It is a new aspect of reduction and silanes such as say you have R3Si and there is a hydrogen attached. So, such reducing agents have been utilized in organic chemistry and we will see what they are and how do they function. Now, the useful reducing properties of diborane for example, B2S6 are essentially due to the monomeric borane and these monomeric boranes can be prepared as say you have diamethyl sulfide borane complex or THF borane complex. So, either we have you have this positive charge here and the negative charge here either we have this complex or this complex they are having or carrying monomeric borane. In addition to these Hc Brown has developed a large number of reducing agents based on boron and 9 borobicyclic nonane or DC amyl borane which we discussed. This is the DC amyl borane and this is 9 borobicyclic nonane are some of the reducing agents based on boron which are not dimeric because of the steric bulk and they need not be stabilized like dimethyl sulfide or tetradofuran are very useful reducing agents and they are bulky reducing agents and they offer similar type of reactivity as normal borane but then with a modified reactivity in terms of steric hindrance. Since, electronegativity and ionization potential of silicon is close to boron. So, as you can see here 1.90 and 2.04 and 8.15 electron volt and 8.30 electron volt. So, they are very close to each other the silicon and the boron. Therefore, suitable derivatives of the pyrophoric gas silane. Now, if we start analyzing BH3 which is existing as B2S6 and if we compare it with SiH4 there is a problem. The problem is that this is like a low boiling gas and of course, it catches fire. B2S6 can be stabilized but this is not stabilized easily and therefore, although there is a comparison in terms of electronegativity and ionization potential it is not easy to use this silane as a reducing agent as a gas. But then there are many modifications just the way such modifications have been done for the boron they have the chemists have also done the modifications on the silicon and a variety of silane derivatives have been introduced to act as hydride donors. This is of course, as I mentioned in view of the fact that SiH4 is pyrophoric and difficult to handle. Now in most of the cases they act as hydride donors but in some cases it has also been found that some of the silicon derivatives act as hydrogen transfer agents in radical passion. Now the commonly used silanes which have got a lot of popularity include triethylsilane of this kind for example of this type triethylsilane then phenylsilane which has a structure of this kind that means 3 hydrogens have been replaced by the phenyl group or diphenylsilane of this kind where two hydrogens have been replaced by two phenyls and of course, diphenylchlorosilane in which one of the hydrogens has been replaced by the chlorine and of course, two hydrogens have been replaced by the phenyl then you have trichlorosilane and then of course, tetra phenyl disilane of this kind and in a similar fashion there is one a very interesting reagent which is trichlorosilane which is what is the trichlorosilane which is basically hindered. So, these are the various kinds of silanes which have been introduced in order to avoid the usage of pyrophoric SiH4 and of course, these reagents are relatively easy to handle. A few examples that are shown here where silanes can be used as reducing agents are like for example, one starts with a tertiary alcohol and in the presence of H+, now we can carry out reactions of different types of silanes very easily in the presence of acid they are not affected and because the silicon hydrogen bond is not ionic it is covalent and therefore, it is easy to carry out the reaction under protein conditions and as you can see here if you take a tertiary alcohol the hydride is transferred from the silane to the carbocation which is what is going to form here as like this and to this the hydrogen from the silane say for example, R3 prime here is transferred to this to this and the product is this form. Now this particular cation which is formed here would obviously has to be taken care of so the positive charge that is going to form here will react with the nucleophile present in the reaction medium which can be water or it can also original alcohol so one can expect this to form but essentially this is what is going to form this can form a little bit if the alcohol allows the reaction to take place on the silicon plus. As you can see here the this is the benzylic alcohol here and it is relatively easy to form the corresponding benzylic cation and once the benzylic cation is formed so you have a relatively stable benzylic cation and that benzylic cation then gets reduced here although it is a primary cation but it is benzylic therefore reduction gives this particular product. Now we can see such a reaction occurring on a primary bromide but having a cyclohexane ring system I am very sure that most of you know what this reaction is going to be going through is if we form the corresponding cation here which is what is going to happen when this bromide reacts with a Lewis acid like aluminum chloride so the aluminum chloride will take away the bromide ion from here and will generate the corresponding primary cation but then this primary cation immediately undergoes a hydride shift 1 to hydride shift leading to the formation of the corresponding tertiary cation and then this tertiary cation as you can see that can react with triethylsilyl having a deuterium so it is a isotope of the hydrogen which allows the introduction of a deuterium atom at this junction. So we can easily get the corresponding deuterated molecule using triethylsilyl which having deuterium. We can also see as similar type of carbocation based reactions if we start with a cycloheptyl bromide they got 39% of the direct reduction and 26% after the rearrangement that means here again one can expect the cation to form in here but then there is a shift of this particular bond to form a primary cation which is what would look similar to what we did it earlier and then this leads to again carbocation shift and forming this tertiary cation and that is what is leading to the formation of this particular molecule in 26% yield. But it is interesting to see that if we take a simple one pentene so something like this if we take here 1, 2, 3, 4, 5 this does not get reduced because we do not have a strong possibility of generating a stabilized or stable cation. On the other hand if we take one methyl cyclohexene it can easily form the corresponding tertiary cation something like this where the positive charge is here and the reduction can lead to the formation of such a molecule. So there is a contrast between the two of them this cannot form a stable cation whereas this can form stable cation and therefore the reaction takes place. So what I want to apply here is that the reduction of molecules which are easy to form a cation can easily give the reduction reduced product and one can get the corresponding deoxygenated product. If it is from an alcohol or if it is from a halide then obviously it is also a replacement of the carbon halogen bond with carbon hydrogen bond. If we take the triethylsilane and we use rhodium reagent or a catalyst then it is found that it proceeds via an enol sallel ether that means the reduction does occur at this junction because it is now modified reducing agent and it forms the corresponding enol sallel ether which upon hydrolysis it gives the corresponding ketone where there is a hydrogen attached here. So there is a hydrogen attached here. Now how does this reaction occur we would like to see So if we take an enone of this kind and react with a silane reagent in the presence of this Wilkinson catalyst then it is found that these two different types of reducing agents were basically utilized and they lead to two different types of products. For example, the first reducing agent in which there is only one hydrogen that means this particular reagent contains one hydrogen and that gives the 98% of the corresponding saturated ketone via obviously enol sallel ether that means this reaction must be going via the enol sallel ether and this gives the corresponding ketone. So this is the intermediate that must be formed. While in the second case when there are two hydrogens Ph2SiH2 it is seen now that the reduction takes place directly onto the carbonyl carbon. In this case the reaction had taken place at the fourth carbon here. So we have to see that how does it happen. So if we have this catalyst rhodium catalyst and react with any silane this is what we are expecting to get it where r3 can be these 3 Rs can be 2 Rs and one more hydrogen or whatever. So when this particular modified reagent interacts with the enone it is proposed that this interacts with the rhodium here through the oxygen and immediately there is a carbon rhodium bond forming such an intermediate. Now this is the first intermediate that can form. Now this intermediate can be in such a way that this particular part of the intermediate can go to the fourth position that is on the other end of the double bond forming this intermediate where if the hydrogen is transferred to this carbon then we get this intermediate which is 1 4 addition and after hydrolysis here H plus water can give this ketone.  So you can have either a 1 2 addition or a 1 4 addition if we invoke such intermediates. Now we see now how it is happening. What has been suggested is in the case of dye and trihydrosilanes that means if we have more of hydrogens attached the bulkiness of the siloxy group is much smaller. So that means if if this particular part is considered and if there are trihydro dye or trihydro that means we are talking about R H 2 Si O kind of species we are talking about it or trihydro you have H 3 Si O part of it that means the bulkiness of the siloxy group is reduced is smaller than that one can think about monohydro silane. So for example if you have here R 2 H Si O so you have two of the R groups and only one hydrogen here so this is a monohydro silane this is a dihydro silane this is a trihydro silane. So the bulkiness of the siloxy group is much smaller in these cases compared to monohydro silanes. And the hydride shift is easier since the participation of the polyhydro silanes in the hydride migration step is much easier. Like for example if we have something like this then the hydrogen is immediately migrated here than of monohydro silanes either by steric reasons or by reactivity for oxidative addition. Thus one to addition takes place. So in such cases where the bulkiness is reduced we get the hydrogen transfer because there is not much steric intense and therefore this is relatively stable and immediately hydrogen is transferred. Now one to addition takes place exclusively especially when the pyrolyhydrosilanes are used in high concentration. So you use you allow this where the R 3 groups are more of hydrogens and therefore this is relatively stable there is not much steric intense and it goes. In the case of monohydro silanes when there is hydrogen only is one present that means on the rhodium there is only one hydrogen has come from the silane that we have used and R 3 is larger groups both the steric and through bond electronic effect of silane group on the nature of the allylic system with regard to the relative ease of isomerization. Now this is particularly isomerizing to this why it is isomerizing while isomerizing this particular carbon rhodium bond is breaking and going to this one here during the process there will be a delta positive which is generated here which is an allylic system that is what is allowing it to migrate and also the steric hindrance the steric hindrance between the siloxy group and the rhodium part is large when it is nonohydrogen containing silane and therefore the steric hindrance allows it to move and away from the system and it goes to the other end of the double bond and also during the process you have delta positive that delta positive will be stabilized by the double bond as well as by the silicon through a beta silicon effect and therefore thus we get the 1, 4 addition exclusively especially when monohydro silanes are used in low concentration. So this is how the reaction is perceived and the reaction occurs in a way that we can tune the reducing agent and therefore you can have either 1, 2 reduction or 1, 4 reduction. We can also carry out reductions of ketones or aldehydes using triethylsilane and for example if we take a ketone of this type with triethylsilane in aqueous medium if we have an acid then of course we get the corresponding alcohol and triethylsilanol as the byproduct and in a similar fashion if we take the ketone and reduce in the presence of an alcohol like R2OH then under acidic conditions with triethylsilane what we get is the corresponding ether and again triethylsilanol comes out as the byproduct. The way it has been perceived or rationalized is that the ketone under acidic condition gets first protonated and the water attacks on to this particular carbon atom and then one forms the particular dihydroxy compound geminal dihydroxy compound which is unstable of course it will be in equilibrium with the ketone. Now if one of the two hydroxy groups say for example this one gets protonated then what one could expect to get is a oxonium ion of this kind by the loss of water. Now this particular oxonium ion then can react with triethylsilane and get reduced to lead to the formation of this particular alcohol and of course triethylsilanol will come out. In a similar fashion if we take this ketone and react with an alcohol in the presence of H+, then of course what we expect to form is a hemiacetal of this kind because proton will protonate the carbonyl oxygen and alcohol will attack as a nucleophile to form this hemiacetal which can of course lose water to form this oxonium ion similar to what we saw it here but now we have this OR2 in the molecule and now when this oxonium ion gets reduced with triethylsilane then of course we get the corresponding ether and of course we will get the triethylsilanol as the byproduct. Now this is how the triethylsilane has been utilized for the reduction of carbonyl compounds under different conditions but in addition to triethylsilane or different kinds of silanes people have also started using polymethylhydrocyloxane PMHS which is shown as like this here and it is a relatively inexpensive non-toxic air and moisture stable liquid it is of course a polymeric liquid and it has been found to be an effective hydride reducing agent as an alternate to monomeric silane reducing agents such as triethylsilane. So we will see how the reactivity of this PMHS can be utilized for the reduction of different kinds of substrates. So till the next class we will stop it here and we will then discuss other aspects of this PMHS and other reducing agents in the next class till then bye thank you.


these negotiations between the Baltimore Ravens and Lamar Jackson I know nobody's tired of hearing about him right of course not but anyway as many reports and rumors and stories and this and that that we've heard a big question that has continued to be asked is who has more leverage who has the upper hand right now when it comes to these negotiations some people feel like it's the Baltimore Ravens some people feel like it's Lamar Jackson some people feel like hey I ain't nobody winning this whole thing right now but let's look at this question from my guy the one and he said everybody says Lamar has the leverage when it comes to the contract situation but I disagree him me out let's just say Lamar gets an offer sheet and the Ravens don't match it he goes to a team that is terrible and just because he's the high-paid quarterback they're going to expect instant results if a team wanted Lamar they would have came after him by now now first let's go to that first part first so if he goes to a team that is terrible just because he's the high-paid QB they're gonna expect instant results with Lamar Jackson yes they will definitely expect instant results and I think that they will get instant results but even still safe instance they didn't get into the results he won he gets paid he gets his bread he gets his money he gets a nice contract and one that he negotiated with whatever team that could be so it would obviously have to be something that he accepted and he liked and he agreed to for him to sign an offer sheet with that team so he will win based off of that alone that'll be a win for him and for the Ravens because they will get their two first round draft picks so both sides would win in that case now in the long run what would the Ravens do at the quarterback position that scares me that frightens me as a matter of fact that is very very scary yeah you have two more first round draft picks over the next two years so you get an additional one this year an additional one next year still be very scared cuz with Lamar anyway you don't know not know anyway you know who he is you don't know his full potential because you haven't tapped into it yet but you've seen a lot of potentially great stuff from him but now if you go the unproven route that's that's a very scary territory to be tiptoeing around so we'll see anyway he said if a team wanted Lamar they would have came after him by now hmm that part I disagree with because teams could be trying to strategize this thing to put the Ravens in a tough position there could be teams that wait until after the draft there could be teams that want him now they could be teams that don't want him now but after the draft maybe there could be teams that are waiting and be like all right Ravens are made there their draft picks and whatnot they trying to size up the team they done signed a couple people here and there and whatnot but oh we got something for them after the draft because you gotta you gotta sign your draft picks right so that's gonna be some more money taken away from the Ravens pot from their salary cap and the team could be plotting so it's tough because it's one of those things that we won't know till we truly know anyway he said Lamar is a great talent but oh yeah you know what this is going Lamar is a great talent but if I'm a franchise like most of teams that needed a quarterback they signed a cheap bridge quarterback and they will draft and develop a rookie quarterback why sign Lamar if you know your team has more needs than quarterback and getting Lamar won't guarantee you a championship so why draft the quarterback why draft the unproven guy it's the same thing right just a different pace scale we as Baltimore Ravens fans know everything that Lamar Jackson brings to the Baltimore Ravens and they still do have needs other needs on the team but we've seen Lamar Jackson while he's not the perfect quarterback we know that no I mean no quarterback is but he covers up so much for the Ravens he covers up a lot so yeah you can have other holds on your team you can have other needs on your team but Lamar Jackson he takes care of a lot of stuff for you now my hope for him whether it's with the Baltimore Ravens or it's with somebody else I really do hope I really hope that wherever he stays or goes that it doesn't just have to be all on him and not that it's all on him now with the Ravens but a lot of stuff is on him a lot and not just regular old franchise quarterbacks a lot of extra stuff that doesn't need to be on him is on him and we understand he's special we know Lamar special but try to make his job easier I mean that that should have been taken care of throughout the past couple years but anyway he said Lamar won't guarantee you a championship what quarterback will I mean I got two of them already but no quarterback guarantees you a championship they don't but anyway he said the only team that needs a quarterback and would be ready to compete for a championship right now in my opinion is the Jets but they're about to go all in for Aaron Rogers man whoever ends up being a quarterback for the Jets boy you gonna have a nice setup and they still talking about Ezekiel Elliott they still talking about Odell Beckham Jr like they been going crazy with it man they just Simon Cole harmony guy Alan Luzardo got Garrett Wilson they not done they already had a real nice defense like just been going crazy with it man so whoever ends up being a quarterback there and Rogers are not like you are set up nice still got Breeze Hall it running back to came forget about him anyway let's continue he said if I was a GM I would build my team develop my rookie QB and use all the cap money left to build my team around an inexpensive rookie QB option like we should have did deal with Lamar you know what I am so glad that you said that I am so glad you said that because I was getting ready to be like well that's what they should have done already but you said it so I appreciate that and this all goes back to just this whole situation is this it's so much frustration because so much of us have been thinking about what should have been done what could have been done what we talked about in the present time well when it was the present time back then on how the Raven should have capitalized but they didn't they didn't and now we're here then there's this standstill there's this impasse so to speak and both sides don't seem like they budging right now so we don't know how this whole thing is gonna end but you got a lot of people feeling like oh man now the Raven since they got Lamar Jackson on a franchise tag they can't make any move they can't get this wire see if they can't get that player they can't sign nobody since Lamar Jackson is on a franchise tag but then you got so many people that forgot like hold up this is the first year for the franchise tag where were all these moves before where were all these moves when he was still on that rookie contract where were all these moves in the last two years of his deal where were the last where were all these moves it with the fifth year option where all these moves the last three years of the contract that he's been on with the rate what was it then it wasn't there so I just don't understand how people have been getting up in arms so yeah this is Lamar's fault that they can't do anything they ain't do anything when he was cheap they ain't do enough when he was she I can't say they didn't do anything but they didn't do nearly enough when he was cheap now he's expensive and they looking around like oh man we ain't got it you had it and you ain't do nothing so now we in this situation and this whole thing like I mean what's funny about this whole thing is that um we talk about it all the time man conversations back and forth and stuff I know a lot of Ravens fans been saying oh man I'm losing sleep is stressing me out I don't know what's gonna happen and then you go then you go on like Lamar Jackson story or something he over there bowling he over there bowling dancing just having a good time and I love it he over there taking pictures in the big red shoes just having a good time man obviously he's doing negotiate or the whole thing he's still doing negotiation or not and handling the business side of stuff but he's still having a good time and that's what matters right anyway he said um this is just my opinion so yeah that was a fun it's a fun one for sure and I appreciate you the one for how you broke it down and everything but yeah I mean this this whole situation this whole scenario is just who I don't even know what to call it man I don't know what to call it I can't call it it's just it is I can't even say it is what it is because we don't even know what it is we don't know what it is we don't know what the next move is gonna be I'm sure tomorrow we're gonna hear a new story a new report on something cuz y'all know I go like if it ain't every day that we hear something new about this then it's definitely Monday through Friday we hear something new every Monday through Friday so tomorrow I expect to hear something new like oh and then we just have to go from there but I don't even know what to say after that more he's a fan and he liked the Ravens and you know I'm a fanatic you see we got the magic and yet my boys are savage and open challenge and madden making rage quit exit out the door use his favorite team with up all the more


Yeah, this is Brett and this 2015 GMC Sierra 1500 Crew Cab 6.5 foot short box is stock number 21J202C. We are here at Summit Automotive in Fond du Lac, Wisconsin, near new and used like-duty truck headquarters. This 2015 GMC Sierra 1500 has the 5.3 liter V8 gas engine. This truck has been fully safety and inspected by our service shop. As a fresh oil and filter change, all the fluids have been checked and topped off and this truck is 100% ready to go. We're going to go inside underneath, start it up, take a look under the hood in this video. Onyx Black is the color and we shoot all of our videos in 1080p, 60 frames per second. So if you have HD capabilities on your computer, tablet, smartphone, or television, I highly recommend turning them on right now because it is your best way to check out the quality condition and options of the truck before seeing it in person. And if you like the video on how we do things here at Summit Automotive in the upper right hand part of the screen is a link to subscribe to our YouTube channel. Click that and then click the bell notifications. You'll get updates on the videos we do each and every day here at Summit Automotive. This one comes with these steel rims with chrome covers and it has Cooper Discover AT3 tires. These are LT26570R17s and they are like new. I'd say 90% of the tread left on them. Front fender is in nice condition. I didn't see any major dents or dings on there. It does come with the projector lamp headlamps. Front bumper is in nice condition. I didn't see any major dents or dings on there. And the headlight lenses are nice and clear. The hood is in nice condition as well. No major dents on there. Paint is very glossy. Passengers side front fender. Excellent shape as well. And the passenger side rim no scuffs or scrapes on there. As you go down this side of the truck take note of how clean the body is, how reflective and mirror like that paint is. We take these HD videos so if you are far away or even if you're close by and just cannot make a trip down but you're still interested in purchasing the truck you can see the truck, hear the truck and have confidence in the vehicle that you're looking at before you even get here. So when you do get here there's absolutely no surprises and you can make a smart and informed buying decision before seeing the truck in person. And if this video helps you make that decision let your salesman know that you saw the video that it was helpful and that Brett sent you. Back rim is in nice shape and the back tires are just as new as the front tires. Frame and underbody, pretty nice shape. Just a little bit of surface rust on the frame there. Two beds, pretty much how they all look. Little rockers and cab corners are in excellent shape. I didn't see any corrosion on them. And down the passenger side box I didn't see any dents, I didn't see any dings. And the paint's in really nice shape. Coming around to the back rear bumper does have a couple little dings there. It does have the rear bumper steps. Full towing package which includes a receiver hitch four pin and seven pin wiring. And the tailgate is in excellent condition. I didn't see any dents or dings on that. Does have a locking tailgate. Spray and bed liner. Beds in pretty nice shape. The bed liner is in nice shape as well. Coming around to the back of the vehicle or to the driver's side I should say. Box looks really good. And for full disclosure this back rim very nice as well. That tire has just as much tried as the rest. Driver's side doors look really good. Inside the work truck package gives you the gray cloth interior. There are no rips or tears. You do get the 40-20-40 split bench seating in the front here.  We'll hop inside check out the miles, radio, and everything that this truck has to offer on the interior. This one comes with 63,367 miles on it. Digital speedometer, insert cluster is pretty nice and clean. You do get cruise controls on the left and a six speed automatic transmission with the optional tap shift. You get AM FM radio on here and you can connect it to a bluetooth phone as well. Climate controls, those outside mirrors are heated. Stability control, cargo lamps, passenger's side and center console floor are in nice shape. No rips or tears on the passenger seat and the headliner is in nice condition as well. You do get map lights up there and we'll take a quick look at the back seats and then we'll start it up and take a look under the hood. Back seats are just nice as front seats, no rips or tears back here. It does have the latch child safety system, fixed glass rear window and you do get the heavy duty rubber floors back here as well and they're in nice shape and side curtain airbags on this truck. Bottoms of the doors all look pretty good. Didn't see any corrosion on them. We'll start it up, take a look under the hood. Starts right up, no check engine lights or anything like that. I would personally like to thank you for checking out the video today and hopefully from this HD video you will have been able to verify the quality and condition of this truck all the way around inside and out. Under the hood we have the 5.3 liter v8 gas engine. Engine bay is very clean, runs very smooth. Once again this truck has been fully safe and inspected by our service shop. Has a fresh oil and filter change. All the fluids have been checked and topped off and this truck is 100 percent ready to go. There is your emissions sticker, projector lamp headlamps and for the age of miles on this one really nice condition and to see more pictures of this truck or one of our other 450 new and used cars, trucks, scvs, minivans, wranglers, halftones, three quarter tons, one tons you name it. We got to go to that website right there, www.summitauto.com. Full pictures and descriptions of every single vehicle from two locations all at www.summitauto.com and if you'd like to check out more HD videos you can go to www.youtube.com slash www.summitauto.com. Remember to like, subscribe, and share on this video and all the videos that you see there. Click the bell notifications you'll get updates on the videos we do each and every day here at Summit Automotive. In fact in a second you will see a link to subscribe to our YouTube channel in the upper left. Link to more GMC CR1500 truck videos like this one in the upper right. Link to this vehicle on our website in the lower left and link to one of our latest YouTube videos in the lower right. Click those checks out. We're super excited to help you with this Ultra Clean 2015 GMC CR1500 crew cab long box work truck in Onyx Black Crew Coat. Thanks again for checking out the video. Remember to like, subscribe, and share.