Okay. When we left off on Friday, we've been talking about alkali, metal, organometallics, alkylithiums, potentially alkyl-sodiums or alkyl-potasiums. You won't see those. But alkylithiums, you'll see a lot of. And we brought up this problem that alkali, metal, organometallics aggregate. They always aggregate in solution. They don't exist as monomers. Even in THF, which is a coordinating solvent, this demand of lithium for extra electrons causes it to do this weird stuff. So if you put butylithium in THF, it adopts these cube-shaped structures. That's the structure of butylithium in THF. And it's an equilibrium in THF with this dimeric form. So not a cube but a square. So each butylithium, each carbon atom here has not just four bonds but five bonds to the carbon atom. As long as it doesn't violate the octet rule, that's okay. So you can see what's happening because of this demand, the high nucleophilicity of this carbon-lithium bond and the demand of lithium to satisfy the octet rule. You get these weird aggregates. So this is not the exception. This is the rule. And so we're sort of stuck in this situation that we want to be truthful about our representations. And so what are we going to do? And so let me show you some heartening stuff for us as arrow pushers.  So we're going to very soon get into the chemistry of pi bonds, of enolates, of azillion things that are very similar. And let me just point out that when you put a lithium enolate in THF, so you make lithium enolates with strong bases like lithium to isopropyl amide, you deprotonate at the alpha position. And how are we going to represent this kind of lithium enolate? Over 99% of this lithium enolate exists as a dimer in solution, kind of like the one I'm showing you over there. And so here's what is true. If you take this and you treat this with benzyl bromide, just to do an SN2 reaction where you displace the bromide using the lithium enolate. So I guess maybe I should draw out some sort of an arrow pushing mechanism, although that's not that important.  How are we going to represent this species, this lithium enolate, when in fact it exists over 99% in solution like this?  And I'm not going to draw the THF molecules on those lithiums. This is not a Lewis structure. These are dative bonds because right of oxygen has three bonds that have a positive charge. So these are dative bonds in here. I'm ignoring the charges. So this is what lithium enolates look like in THF. And these striatwizers showed that even though this is 99% of your lithium enolate in solution, that small amount of monomer that's floating around is actually what's doing the chemical reaction. In other words, if you want to draw the correct arrow pushing mechanism, you ought to be drawing the monomer in there. Even though that's not most of what this lithium enolate looks like, we're going to draw all of our organometallic reactions. Alkyl lithiums, lithium enolates, drawing the monomer. So never forget that these aggregates are present in your solution, but when you draw arrow pushing mechanisms, just draw the monomer and do the same kind of arrow pushing that you've been doing since sophomore organic chemistry. And that's going to be our rule for this class.  For arrow pushing, ignore aggregation. Just acknowledge that it's there mentally, but when you push your arrows, just draw the monomers.  This is the way we're going to do our arrow pushing in this class because, and again, we find some justification from this important study of Schreitweiser showing that it's the monomers that are doing the business work there. Okay, so that's our rule for alkyl lithiums, for enolates. Just draw the monomer. Okay, so let's go ahead and cover the last little piece of our puzzle here for, and this is really not an alkali or organometallic, but I want to contrast alkyl lithiums and alkyl sodiums with one class of organometallic reagents. And that's not having lithium or sodium on the carbon atom, it's having copper. And so let's talk about two types of organo-copper reagents. So the first type we call just simple organo-copper compound, and it looks like this. So this would be a copper one with some alkyl group attached to it. Could be butyl, could be phenyl. So if it's phenyl, I'd call it phenyl-copper. And one characteristic of simple organo-copper reagents is they don't do much. You'd have to have something very reactive to get it to be worth your while to make this organo-copper reagent. So organo-coppers are not very interesting. And let me contrast that with a cuprate, which is very interesting and very reactive. Here's a cuprate, an organo-cuprate typically looks like this, and guess how you make the organo-cuprate? You make it the same way you make the organo-copper reagent. So an organo-copper reagent, you take copper bromide and alkyl lithium, you mix them together. But if you add a second equivalent of the alkyl lithium to your organo-copper reagent, now you can imagine how this alkyl can again add to copper. And so now you have two alkyl groups on copper. And these are very nucleophilic and not very basic. And if you were as interested in CC bond formation as I am, then that's an interesting set of properties, things that are very nucleophilic and not very basic. Okay, so let's just go ahead and talk about how to think about these.   But we're going to draw these like this if you ever need to. So this little suffix ending here, 8, cuprate, tells me there's a negative charge on copper. That tells me that the bonds to copper are nucleophilic. So it doesn't actually look like this. It exists as an aggregate. But you can just pretend it looks something like this, where I've added a second alkyl group to my organo-copper reagents and now there's two alkyl groups on there. And so those bonds are nucleophilic on that organo-copper reagent. So we've seen other eight complexes like hydrido-boreate, hydrido-illuminate, siliconate, it's the same idea. You get this nucleophilicity out of the bond. So one property of cuprates, and I think I can sum this up in a simple statement, all the things that you wish organo-lithiums would do, this is what organo-copperates do. They do substitution reactions with alkyl halides. They efficiently open epoxides to make CC bonds, which alkylithiums do not do. They do 1, 4 conjugate addition reactions. They do SN2 prime reactions. All the arrow pushing mistakes that you make with organo-lithiums, these are the things that organo-copperates are good for. Let's take some examples of some of the things that you can do with cuprates. So let's suppose you wanted to make a carbon-carbon bond there. We have lots of techniques now that involve transition metals and palladium catalysis. But in the days before palladium catalysis, if you wanted to make a carbon-carbon bond here, you can't just do SN2 substitution at that center. Even with copper, you can't. But at least when you mix lithium-dithenyl-copperate in here, you get very efficient substitution. Don't worry about the mechanism. It's not SN2, but you get very efficient substitution of that bromide. And it doesn't have to be an SP2 center. It can be an alkyl halide if you wanted. So I'm just using the vinyl group here to emphasize it. That's something you couldn't do with other reagents, that kind of a substitution process. SN2 prime reactions. Cuprates are good for that. SN2 prime reactions are very unusual. But if you take cuprate reagents, so here I have an allylic bromide. So how do I form a bond to this end carbon and not directly here to this secondary position? If you add some sort of an alkoxide nucleophile, you're not going to get SN2 prime reactions out of that. They'll still add here or else do eliminations. So here, if you wanted to substitute this through an SN2 prime reaction where your nucleophile adds to the end, then you could just add a cuprate reagent. They prefer SN2 prime. And there's my butyl group adding to the end. You know, if I drew some sort of a mechanism for this, this would be completely fictional. But if you wanted to have some way to think about this with arrow pushing, I wouldn't count you wrong if you did an arrow pushing reaction, even if it's completely unrealistic. This will start off with some copper bound to the olefin. But if you did this, I wouldn't complain. Here's what I'm thinking when I say SN2 prime in case you've forgotten. What is SN2 prime? It's when you attack the double bond of an allylic leaving group system. Okay, so those are two examples of reactions that cuprates do. They open epoxides. And I'm not going to draw that, but this is one of those reactions they show you in sophomore organic chemistry when they're trying to teach you that SN2 prime is the best reaction in the world, cuprates are great at opening epoxides and forming C-C bonds and other types of organometallics or not. Okay, the last major class of reactions that cuprates are great at is one four addition reactions. So let me just help you contrast some patterns of reactivity here. If you take a simple enone and you add an alkyl lithium or even a very pure green yard reagent that has no contaminating copper in there. So I'll start off by adding an alkyl lithium. That carbon atom and alkyl lithium has a very significant amount of anionic of negative charge. If you look at the formal charge, there's a partial negative on the methyl carbon right there. And that makes it want to add here to the carbon. You get preferential addition for most simple organometallics to the carbonyl carbon. And so after the, well, I guess I don't need to say after the workup, I'll just draw it as the alkoxide. That's the preferred side of addition. Don't expect to see any one four. We call this one two addition because normally we number the carbons in this enone system. Let me get a red pen here just so we can see the numbering and we can remind you. So one term for this process is we call this one two addition to this enone system. We're changing the bonding to atoms one and two. We also call this conjugate addition. This is the other phrase for this. In contrast, if we add a cuprate to this, lithium dimethyl cuprate, now you see only the conjugate addition reaction here. This is a function of the fact that there isn't a, even though we draw it like this, there isn't a lot of negative charge on these carbons of the methyl group. They're very, those methyl carbon, sorry, methyl copper bonds are very nucleophilic, but they're not very basic. And I don't know why I'm doing this. That looks awful to me. So in this case, those methyl carbon bonds attack in a conjugate addition faction to give you this copper enolate. And the other copper stuff is, so what's the remainder that's floating around before I reconnect things? I've got methyl copper. Remember I said that's not very reactive. That's one of the byproducts. And I have this lithium floating around until I end up with recordination of this O minus to copper and lithium species that are floating around in solution. Okay, so fantastic reaction. It, I could draw an arrow pushing reaction where I simply make the methyl copper bond attack at carbon four. It's not really like that. In fact, the copper starts off bonded, pi bonded to the enone pi bond, the C-C pi bond. But you don't need to worry about that. Just if you want to do arrow pushing where you just take the methyl copper bond and attack, I'll accept that. Okay, so let's talk about one way to make those reactions even better. And this is more of a recipe issue than an arrow pushing strategy for you. And that is that trimethylsiloclide is known to accelerate these additions by copper reagents, specifically by cuprates. And so just to give you a sense for the effect here, it's normally very hard to do conjugate additions when you have this kind of disubstituted beta carbon here. But having those two substituents really slows down additions here. It's very hard. But if you add, take your standard cuprate addition, lithium-dibutyl cuprate, and you add in some TMS chloride to that, it phenomenally accelerates an otherwise slow reaction. So you can imagine that the silicon is pre-bonding to the carbonyl oxygen, making the system more electrophilic. And again, the precise mechanism, I don't want to go through that in any detail simply to say that generally when you see people doing, conjugate additions with any sort of steric challenges in there with cuprate reagents, there's usually TMS chloride in there in order to help you accelerate that. And the product is not the lithium enolate, you get something called a silil enol ether. And we'll talk more about silil enol ethers later, which have their own benefits. Okay, so the last sort of dramatic example of the effect of this combination of TMS chloride and cuprates is even enols, aldehydes are so reactive. We talked about the rates of addition of aldehydes versus ketones. We talked about the thermodynamic ease with which you can pyramidalize at aldehydes. And so it is very hard to keep nucleos files from attacking aldehydes and to get them to attack that beta position on an enone. And if you use this combination of TMS chloride and cuprate, you favor, you still favor addition to the beta carbon over addition to the aldehyde carbon. So that's phenomenal. It's phenomenal that you can get that kind of selectivity and not attack that aldehyde. Okay, I've got one last sort of not alkali organometallic here in this lecture that's called alkali organometallic. Just to get you, so I hope when you see a copper attached to carbon that you don't mistake that for the same reactivity as an alkyl lithium. That's been the point here. Don't mistake dialkyl cuprates as organolithiums. The reactivity is very different. And here's one last type of organometallic and that zinc that has none of these basicity issues of an organolithium reagent. And this particular example will convince you that the alkyl zinx are very different. They must be very different from alkyl lithiums. So I'm going to start off by showing you, it's very easy to make acetals of cyclopropanone. Cyclopropanone hates to exist as the ketone. You can't buy cyclopropanone, but you can buy acetals. They're very cheap and so you can even buy the monoethoxy adduct of cyclopropanone and it's very easy to sililate that OH. This is probably commercially available as well. Whenever I see a cyclopropane and I hope you're thinking is the same, I think gee, those bonds have so much p-character. I want to start using those bonds as nucleophiles. They're nucleophilic. There's lots of p-character in those bonds. And when I see lone pairs here on these oxygens, I'm thinking gee, those are donating here into this antibonding orbital. Let me make it end precisely on this antibond. Those lone pairs on these oxygen atoms are souping up the nucleophilicity of these two C-C bonds. So if I thought a cyclopropane bond was nucleophilic and I see an oxygen lone pair nearby, I ought to think that's super-duper nucleophilic. So when you treat this with zinc chloride, just buy some zinc chloride. You typically get it as a hydrate, dry it off, put it under vacuum and heat it. What you'll find is when you mix zinc chloride in there is that bond, that C-C bond that's strained in nucleophilic will attack the zinc chloride. And so you get this very weird-looking structure. And I'll start off by drawing it like drawing the initial intermediate. But this doesn't just sit there like this.  Imagine the chloride popping off and then coming back in and displacing silicon. That's not a one-step process. It's three steps. Don't worry about the number of steps. Ultimately what you get is this very strange-looking reagent that at first glance looks okay. It's got this nice sort of chelate structure in there. You can imagine what I'm going to do with those carbonyls in just a second. But what's amazing about this structure is it looks kind of like an enolate, but it's not an enolate. There's an ACH2 group here. Let me just draw those H's so we can clearly see them. In other words, I've got nucleophilic bonds and I've got electrophilic carbonyls built into the same reagent. What is amazing is that these bonds are not so nucleophilic that they go around attacking other carbonyls. Alkyl lithiums attack esters and carbonyls. These carbon zinc bonds are so unreactive that they don't go around attacking the carbonyls in other molecules that are floating around. Right? You have more than one of these in solution. These carbon zinc bonds don't go around attacking the ester bonds in your carbonyl. You can isolate these types of reagents. So what are these alkyl zinc reagents great for? If you have superduper activated aldehydes, they'll attack them. If you have palladium complexes floating around, these bonds will attack the palladium complexes. And you can transfer those alkyl groups to palladium. That's where they tend to be useful. So this is just to convince you that these types of bonds are not at all nucleophilic and basic like an alkyl lithium. So much, much, much attenuated reactivity. It's extraordinary that you can have esters in the same pot as those alkyl zinc bonds. Okay. So that's all we're going to say about alkyl sodium, alkyl potassium, alkyl lithium. Dialkyl cuprates, alkyl zinc species. And you should be getting lots of practice using those as nucleophiles to attack things. So we're going to have a major switch in years now and start talking about pi bonds as nucleophiles. We've spent all kinds of time talking now about lone pairs as nucleophiles or bonds to lithium as nucleophiles. And so let's change what we're doing. So we're going to talk about adding electrophiles to carbon-carbon pi bonds or conversely, like I said, we're going to talk about pi bonds as nucleophiles. And these are the most important carbon-carbon bond forming reactions or the most important class of bonding reactions in the field of organic chemistry. Or maybe I should say organic synthesis. Okay. So we're just going to talk about over and over again, over and over and over. We're going to talk about that. That's what we're going to talk about. So I want to start off by helping us establish a picture, an MO picture of the pi bond or various types of pi bonds. And what I want to do is I want to contrast these types of pi systems. There's three different pi bonds. And we're going to see all kinds of reactions where these act potentially as nucleophiles. Here's what we're going to see a lot of. If I take some sort of an electrophile, like a carbocation, and I think about that addition, that explains electrophilic aromatic substitution and all those other, there's so many reactions that that explains.  And it doesn't matter what the electrophile is. It could be a proton, like an acid. It could be a carbocation. It could be aluminum. Right? That's not the most nucleophilic part and basic part of that molecule. We've said this over and over. When you react with carbonyls, I want you to use these. Right? That's what I want you to use. And those aren't the same. You might think they give you the same thing. Oh, they give me the same sort of resonance. But this pi bond is not as nucleophilic as those lone pairs on a carbonyl. So you use the lone pairs. And it's, if that were true for oxygen, it's doubly true for an amine. Right? That's the nucleophilic part of an amine. That's the basic part of an amine, not the pi bond. So use the lone pairs. Now, of course, with carbon, you don't have lone pairs on carbon, so with double bonds, you're going to use the pi bond. There's no choice with that. Okay, so just keep that in mind. Let's come back and talk about trajectory here. And I want to distinguish additions to carbonyls because we went into so much detail about the correct trajectories for addition to carbonyls. We said there was this thing called a Berge Dunnitz angle that honors the fact that pi star looks like this. Pi star has this sort of phasing picture that looks like this. And if I'm a nucleophile trying to overlap with this empty pi star orbital, if you're a nucleophile adding to some sort of pi star, and I'm going to arbitrarily phase my nucleophile to have some empty orbital like this that's unhashed, I want to minimize my interactions with these hashed lobes of pi star. Those are destructive bonding interactions. I want to tilt myself around so I don't have any interactions with these oppositely phased orbitals. And the only way to do that is to attack from this 109-degree angle, the Berge Dunnitz angle. But things are totally different when we add electrophiles to CC bonds. So if you're an electrophile, you're not adding to pi star, for an electrophile, it's opposite. This thing is the nucleophile. The CC bond is the nucleophile. And so if I draw this sort of orbital picture, I'll decompose this pi into the individual p orbitals. Now if I want to maximize the interaction of this pi bond, which is now the filled orbital in the nucleophile, and I'll have some sort of fictitious empty orbital here, now I do want to maximize the interactions between both of those lobes. The prediction is that when electrophiles attack pi bonds, they should approach from the middle. You simultaneously will get bonding from both of these carbon atoms to both of those carbon atoms. You can't avoid that. As close as you get to this carbon atom, you're also going to be somewhat close to that one. And both of those interactions are going to lead to bonding combinations. Okay, so there's a trajectory difference between adding electrophiles to pi bonds versus adding nucleophiles to pi bonds. So 109-degree angles here, whereas here you approach the middle of the double bond. That's the expectation. Okay, so let's skip for a brief moment back to an old idea. What I want to do is I want to contrast two different types of elimination geometries for you. And we'll take this sort of fictitious example here where I have, and it doesn't have to be a chloride leaving group. The leaving group really doesn't matter. It could be protonated water ready to leave. But if you contrast these two types of geometries for elimination of the chloride group, the one on the right-hand side, the one on the left-hand side, which one is better? Which one is going to eliminate chloride faster? If I think about where sigma star is located for this carbon-chlorine bond over here, I would expect this one over here on the left-hand side to be faster than this one over here on the right-hand side. So I hope you already know that anti-eliminations are favored over sin-type eliminations. So what we're really saying is that this has a lower energy transition state. The transition state in order to eliminate here is lower in energy than this other transition state. So this transition state is lower in energy to give you that. But what we're also saying, right, even though I could do in theory something like this and get to something that looks very similar or I guess identical, what I'm really actually saying is that if we think about the opposite reaction, if I think about nucleophiles adding to pi star, that transition state, I'm also saying that that transition state is lower in energy. Either the transition state is lower in energy or it's not. That means for both the forward and the backward reaction, this transition state is lower in energy than the one where I attack like this. In other words, when I attack with some sort of a nucleophile on a pi star, that lone pair that appears on the neighboring atom doesn't appear sin to the nucleophile. It appears anti to the nucleophile. It's the same transition state for pushing out a leaving group or for adding. And so here's the big point that I'm making right here. Here's the take home lesson for this that's important. Whenever I have some sort of a double bond and I have a nucleophile that's poised nearby and to make this interesting I'll make this a metal. Let's make this metal carbon bond to the nucleophile. If the metal carbon bond is on top of this pi system and attacking it from the top, what that means is that this pi bond will be nucleophilic on the bottom face. That's a consequence of this stereoelectronic relationship that I showed you above. If I have nucleophiles attacking pi bonds from the top face, that nucleophilicity will be realized and this is really just a resonance structure. Well, that nucleophilicity will be realized on the bottom face. That's the important point. And it's all related to this iminium ion thing that I showed you up above. Okay, so let's take some examples of that. So how does that become useful in organic synthesis or of any consequence? So let me go ahead and give you an example. I'm going to try to draw out as best I can some sort of a cyclohexenol system edge on because I want to see both faces of that, the top and the bottom face of this cyclohexene. And of course, it doesn't make a difference between what is the top face of the bottom face unless I have some substituent there. So just to help me keep this straight, I'm going to put a methyl group on the top face of this cyclohexene. So now if a reaction occurs, I can tell, well, it occurred either on the same face as the methyl or the opposite face of the methyl. And of course, alkenes aren't very nucleophilic. So let me soup this up. Let me put some nucleophilic bond here that's long and nucleophilic. Let's make that tin. There's that long nucleophilic bond. You should now not be surprised after I went through this big hoopla over here about the fact that if I protonate that bond or react it with any kind of an electrophile, let's suppose I protonate that bond. Of course, I can't tell where I'm protonating if I use protons, so let me make this deuterium. So now if I protonate that bond, my expectation should be that if this is donating from the top face and I'm not going to actually move those electrons, but if this tin carbon bond is really nucleophilic and is really souping up, if it's really donating into that pi system and souping up the basicity and nucleophilicity of the pi bond, it ought to be happening more on the bottom face opposite this carbon tin bond than on the top face. And that's exactly true. When you look at deuteration of this exact substrate, what you find is that the deuterium gets picked up on the bottom face. And now I'm just going to draw a D instead of the sort of isotopic symbol. So methyl is on the top, deuterium is on the bottom, and you get this phenomenally stable beta stanyl carbocation with this long nucleophilic tin bond there, and then this acetate is floating around looking for something to attack. And gee, right there is that tin. Now it's not an SN2 substitution, but that acetate is going to attack that tin and pop it off. And so the final compound that you get out of this is that the deuterium is going to be on the opposite face of the methyl. This is really powerful, useful stuff. And we're going to see now a zillion reactions of allyl stananes and allylsilanes and allyl, any metal you want where there's this facial selectivity, the metals on one face, the electrophiles on the opposite face of the pi bond. So just keep that in mind. Okay, here's another example of exactly, so maybe you don't care about protonation reactions. Who cares about that? Protonation is a very interesting process. I would agree with that. So let's extrapolate this a little bit. Let's suppose we take an allylsilane and you had some magical way to make this optically pure. I mean it doesn't have to be magic. And now what you're really interested in is a chemist is C-C bond formation. And so here's my electrophile. You take an epoxide, a simple oxurane, and you coordinate to that titanium tetrachloride. So that now that oxurane is very electrophilic and very easy to attack. So when you see attack, your expectation should be is that the electrophile should come in from the bottom face opposite the silicon. And that's true. That's what you see. Here's the intermediate that you get. And here's this carbocation. I love that carbocation. It's got beta-silicon, silicon carbon bond next door, donating into the empty P orbital and stabilizing it. And I just made a new C-C bond on the bottom face of that system. It's the bottom face of that olefin that attacked the epoxide and opened it up. And I'm not going to go through all the steps here to exchange, but ultimately after you do the workup, what you get is this new carbon-carbon bond on the bottom face, opposite where the silicon was. Okay, so keep that feature in mind. When we have nucleophilic bonds next to pi systems, they're going to make those pi systems more nucleophilic than normal. And there's a facial selectivity to that. So keep that in mind. Okay, so now let's come back to some simple mechanisms that I kind of hope you already know, but maybe not in the detail that I'm going to show you. So at some point during about your fourth or fifth month in sophomore organic chemistry, you started learning about a zillion reactions where you add electrophiles to C-C bonds. Halogens like Br2 or Cl2 or HCl. And so let's come back and look at those reactions that I hope you already know. And so we'll start off by, I'm going to try to draw an alkene here. And I'm going to try to draw this alkene edge on so that we can clearly see that the alkene has two different faces associated with it. So I'm trying to envision an alkene edge on. So now there's a top face and a bottom face to that. And so if I add bromine to this, Br2, you'll end up making the dibromide, the visceral 1, 2 dibromide. And we know that these reactions involve bromonium ions. What does bromonium mean? Bromonium means a bromine that has two bonds. This one just happens to be a three-membered ring bromonium ion. You know, if you just had two bonds to bromine, it would be a bromonium ion. And this bromonium just happens to be strained in cyclic. So these reactions go through this cyclic bromonium ion, this strained cyclic bromonium ion. I'll just write bromonium here. Two bonds to bromine. So how would we push arrows for this? The way you push arrows for this is that we have to show that it's the pi bond that's attacking this BRBR bond. That's a weak bond. It's easy to attack. It's got a low-lying sigma star that makes it easy to attack. The challenge is that as you take these electrons away from one of these two carbon atoms, you're going to leave a carbocation. And that carbocation is not going to be happy. If you start taking away electrons from, say, this carbon, well, isn't there a lone pair that's right here? In fact, three lone pairs that are poised and ready to start adding into that carbocation as we develop it. So it shouldn't be surprising to you that as you're attacking this, you could come back in with these lone pairs and make a second bond. And so that's, this is the traditional way that we depict these, these bromonium ions. And so if we have some sort of a bromide here that's left over, the second part of this mechanism is to come back in and attack on either side. That would give you one enantiomer versus the other. If I attack this side, I'll get one enantiomer. If I attack the other side, I'll get the other enantiomer as long as those R groups are the same. But the bottom line is that bromination should give you an anti, an overall anti-addition of bromine where the two bromine atoms end up getting added from the opposite face. So the two bromides end up anti to each other.   So this is not the correct mechanism in reality. But this is how I would like you to draw it.  But in case anybody ever asks you, gee, didn't anybody ever teach you the correct mechanism for bromination? At least you can say you've seen it somewhere. It turns out that in reality, bromine forms a pi complex with olefins before there's any carbon-bromine bond formation. It turns out there's an initial complexation. And the problem with this is we don't have good Lewis structures to depict these. We have to draw things like dative bonds or sometimes people draw these dashed bonds. So you get this pi complex, sometimes, I'll say also known as a k a, a charge transfer complex. And so what is this charge transfer complex? A charge transfer complex basically means that the pi bond is donating into this bromine-bromine bond and it just sits there with this pi bond donating into that sigma star orbital for the bromine-bromine bond. And there's no, there's no dissociation of bromide initially. Initially they just sit here like this. And then this bromide gets pushed out. So there's a pre-coordination. And we're not going to draw that. We're going to continue drawing this exactly the way that you've drawn it before. Someday you're going to run into some reaction that you can't explain and I hope you'll remember this picture of bromination. So keep drawing halogenation reactions with Cl2 and Br2 in the same way that you've been drawing them. Just use these arrows here to push this. Don't draw it as two steps. But if you ever need to, you can fall back on that picture for bromination or chlorination of double bonds. So if you look at rates of bromination of alkenes and methanol, let's go ahead and talk about how the structure of the alkene influences the reactivity towards electrophiles.  There's no substituents on there. If I put even a single alkyl group on there, I got a 100-fold rate acceleration just by having a simple alkyl group. And if you want some way, I'm not going to go back through and explain this to you, but it's exactly the same as that carbon silo, well, it's the same type of idea as that carbon silicon bond or the carbon tin bond. These bonds, these proton carbon bonds are donating into pi star, they are souping up the nucleophilicity of that pi bond. So that's the effect of having these bonds nearby near that olefin is they soup up this pi bond nucleophilicity. And you don't have those bonds on ethylene. Of course, when I look at a terminal olefin, a C-C double bond at the end of an alkyl chain, I'm thinking that looks unreactive to me. So these are just relative rates of bromination. How fast do these pi bonds attack bromine? This terminal olefin looks unreactive to me. When I think of reactive alkenes, I think of internal olefins that have two alkyl substituents on them. That's a more typical type of substrate that you'll use. And this is another factor of 10, factor of 20 actually closer to a factor of 20 in reactivity. So having two alkyl groups is even more reactive. Just moving the double bond to the middle of butene makes it that much more reactive. And if I rearrange my butene, still four carbon atoms in the right way, now I get even higher reactivity. And you can have all kinds of explanations for this. The way to think about this arrangement, so these both have four carbons and look at the reactivity here, is that here if I think about what this H-carbon bond is doing is it's kind of souping up the reactivity over here. And there's a CH bond over, or three of them. There's CH bonds over here that are souping up the other carbon reactivity. But you'll get higher reactivity if both of these substituents are souping up the same carbon atom. Right? If you want to draw some kind of a resonance structure to help you see that both of these are cooperatively accelerating the nucleophilicity of this carbon atom at the end. And so you see this higher rate of addition. And then the fastest of all these would be a trisubstituted olefin. And the important point here is that all olefins are not equally reactive. And if you've got some complex substrate and you want to do a selective epoxidation of an internal olefin versus a terminal olefin, you will probably be able to get a high yield out of that. So different levels of nucleophilicity when you add electrophiles to olefins depending on the substituents that are on the olefin. Okay, let's go ahead and talk about the intermediates that are involved here. So this idea of brominating a double bond or. So when you draw some sort of a reaction like this, how do I know it's not like this? What's this cyclic bromonium business? Why can't I just make a free carbocation like that? How do I know whether it's going through this cyclic bromonium ion business or whether I'm simply attacking and having a free carbocation? Well, we can check on this. I'll show you how you check. What you do is you look at the percentage of anti. If it really is going through this kind of cyclic bromonium ion, the two bromines will always add anti to each other because the leaving group is on the opposite face of where the nucleophile is attacking. So I'm going to give you a series of olefins and we can see how these substituents affect whether you're going through the cyclic bromonium ion. So in this simple internal olefin butene, you get 100% anti product out of this, anti addition of the two bromides. That tells you that 100% of that was going through the cyclic bromonium ion. But if we put a carbocation stabilizing group, we can tip that balance, right? If we stabilize this enough, we can start to see some carbocation formation. Some of it goes through this cyclic bromonium ion. Some of it goes through the free carbocation. So remember, these are the two choices. Are these lone pairs coming back in and attacking the new carbocation as the bromine adds? Or is the double bond simply attacking the bromine and leaving a free carbocation? And so when we have a phenyl group here as one of our substituents, we see only 83% anti addition. In other words, some of this is going through the free carbocation like this. And if we really substitute, if we add a second substituent to really help stabilize this carbocation at that center, now we see only 68% anti addition. So 68% of it, or at least a significant fraction of this, is still going through the cyclic bromonium ion. Even though we could generate, in theory, a very stabilized carbocation, we're still getting a very significant amount of that cyclic bromonium ion formation. So cyclic bromonium ion formation is the rule. Even when you can form stabilized carbocations. Okay, I'm going to go ahead and stop right there. And we'll come back and say, I feel like I'm going to say almost all the same things when we add HBR and HCl and acids to double bonds.


Harold and Kumar from 2004, quite possibly one of the funniest movies ever made. Hey, what's up guys, it's Josh here. Today I wanna do a little movie review on Harold and Kumar Go to White Castle from 2004. And I haven't seen this movie in a long, long time. For some reason, it's a little bit intimidating to review your absolute favorite movies. I have no idea why. I'm so glad that I revisited this because I watched a lot of films similar to this Van Wilder, not another teen movie. The New Guy. One of my favorites was Van Wilder from 2002. Very solid. I don't know why I didn't do a review on that. But I can say watching Van Wilder, watching Harold and Kumar, I actually watched all three Harold and Kumar's. There is something ridiculously special about this movie in general. And it's just so much better than all the movies at the time. I really like Van Wilder. It's probably my favorite from that post-American pie period, the early 2000s, like party type movies. I really did enjoy Van Wilder. But this one wasn't only better. It was clearly better. Harold and Kumar, I just love it on so many levels. So let's just jump right into the pros. To be honest, it's one of the funniest movies I've ever seen even to this day. It's one of the funniest movies ever made. It is just absolutely hilarious.  And to me, it really is one of the funniest movies ever made. There's a lot of story here. There's a lot of progression. It's a long journey that they go on. It's kind of like a journey of growing up in a way. And you know, they're kind of a little bit timid. By the end of the trip, they've really just grown up and they can handle absolutely anything because they've just had everything thrown at them. I'm a real big fan of road trip movies. And for some reason, the newer movies, I don't know, whenever someone goes on a road trip, I don't feel like I'm going along with the trip. I don't know why. One of my favorite road trip movies is Dumb and Dumber. And you just feel like you're on board with the trip. But then you watch Dumb and Dumber 2. It's a newer movie. It's another road trip type movie. And you don't feel like you're actually on the road with them. It's weird. So these older road trip movies, I feel so much more like I'm on board with them. And this is just one of my favorites of all time. There's so many funny cameos and comedians that pop up in here. You got like Jamie Kennedy. You got Anthony Anderson. You got like Bobby Lee, Neil Patrick Harris, which is a whole funny thing in and of itself. And you even got Ryan Reynolds. All the cameos of people in this movie, not only were interesting to see, but they were genuinely hilarious. This movie has so many memorable scenes. Like even if just a few of these scenes were in this movie, this movie would be hilarious. The jail cell scene is hilarious. The surgeon scene is hilarious. The Jamie Kennedy scene when he stops to go pee is hilarious. The Anthony Anderson scene is hilarious. The whole Neil Patrick Harris incident is hilarious. The whole crossing the street in the middle of the night. All these situations, if they just had that in the movie, it might have been the high point of the movie and probably would have been enjoyable if they just had a few things. But this movie is just jam packed with hilarious thing after hilarious thing. And on top of that, it's a little bit more original than the next two movies because the next two movies, they find a clever way to do a very similar type joke and kind of copy it a little bit beat for beats. But this movie, every single thing they did was unique and hilarious. All right guys, if I were to get into the mixed aspects, and this is kind of with all the movies at the time, it has a mild gross out factor feel. You just have a lot of little things to kind of gross you out. When he gets picked up by the tow truck driver, that scene's a little bit gross. When he comes in and sees Kumar Naked and all this stuff, so there's a lot of these gross out type scenes. This was kind of a popular thing at the time. It doesn't really bother me that much, but it does stand out. It's a little bit more of gross out humor versus today. I don't really the only cons I could really come across with this movie is that it has some bad CGI or not the best CGI. They have a couple of these dream sequences where Harold or Kumar are dreaming and it's not as good as it would be done today, but I can't really hold it against it. I really have nothing bad to say about it. This movie is near perfect. If I were to rate it, I'd probably give it like a nine to a 9.5 out of 10, which is near perfect for me. I really just don't have any flaws with it. Like the story by itself is good and entertaining and worth watching. But on top of that, it's jam packed with things that are actually funny and not just like five or 10 funny things. I mean, this movie just hits you with non-stop funny situation after funny situation. So to be honest, it's near perfect. I would struggle to find a comedy that would be better than this. It's for sure in my top five comedies of all time. And Buy, Try or Pass is 100% a buy for me because I absolutely love this movie. I wasn't really as interested or impressed with Harold and Kumar too. And the third one, it actually killed a lot of the magic that I felt was in this movie. Turn around the road to 50,000 subscribers and I couldn't do it without any of you guys. I hope you guys are the best. I'm having a great day out here. Hopefully having a great day at home. See you all in the next video. Peace.


Hello everyone. Welcome to Options with Doug. Streaming live daily on Bookmap Discord and the Bookmap YouTube channel at 1.30 p.m. Eastern Time. Before I get started I need to go through their disclosures. General disclosure, all book map limited materials, information, and presentations are for educational purposes only and should not be considered specific investment advice nor recommendations. Risk disclosure, trading futures, equities, and options involves substantial risk of loss and is not suitable for all investors. Pass performance is not necessarily indicative of future results. The focus of my presentation and the focus of the Options-Doug chat channel in Discord is options order flow, the impact of options markets on stocks and futures, and the influence of market maker hedging flow on price action. I have a two-step process for trading in the first is planning and I use positional analysis. I look at how traders and market makers are positioned in the options market and how those positions change from day to day to develop a thesis regarding the expected trading range and volatility for the day as well as a directional bias. And the second step of my process is execution and I look at real-time order flow and book map and real-time market maker hedging flow and spot gamma hero to confirm my thesis and for setups for entries and exits. And when I talk about setups I will be talking about an underlying asset and the setups can be taken with futures contracts, shares of stock, or options. Questions and comments are welcome and I will be watching both the Options-Doug chat channel in Discord as well as the chat and YouTube for your questions and comments. And hello Karma FX, glad you're here, welcome. All right my agenda for today. I want to cover news items, economic data, events, and earnings for yesterday as well as the rest of the week. Then I'll go through my positional analysis, then I'll review some setups from this morning and then we'll take a look at the live market. And when we get to the live market if anyone has any stocks they want me to take a look at please let me know and I will do that. Let's get started with economic data, news items. So first of all the of course the big news is the Fitch downgrade of US credit that came yesterday after the RTH close and that has caused quite a move lower in the market today. And then the second news item was AMD's earnings. AMD reported earnings after the close yesterday. There was an initial positive response to that and then that turned around pretty sharply today. So we'll take when we get to setups we'll take a look at AMD today. All right, let's get started with positional analysis. I'm going to start with the S&P 500. This is the ES futures and book map. And before I take a closer look at this chart I want to take a look at a larger time frame. I'm going to go to SBX and hello trade and sale says greetings from Switzerland. That sounds great. I wish I was there. So again hello and welcome. All right, so the SPX gap lower down below the lower daily expected move and traded below the lower weekly expected move and now seems to be trying to recover. We'll talk more about that in a few minutes. Let me point out the levels on this chart. I know with the labels the price action and SPX is difficult to see. The reason I'm showing this 30 day one hour chart is to show all of the key levels that keeps expected move levels as well as the key spot gamma levels. So let me start with the lower and upper weekly expected move shown with the dash purple lines. Note SPX did trade below that and now seems to be trying to recover above that. That's from the options market. And then the next levels, the lower and upper daily expected move again from the options market and SPX gap down lower than the lower daily expected move and probably won't recover that but who knows. All right, let me point out some spot gamma levels. These are proprietary spot gamma levels provided to spot gamma subscribers. And the first is the put wall at 4500. That is the strike with the largest net negative gamma that can be expected to act as support. And the next level up is the 4570 volatility trigger that is spot gammas proprietary gamma flip level. Below that level market makers position on the gamma curve is negative in a negative gamma environment. Market makers have to trade with price to hedge their delta exposure and that tends to enhance or increase volatility. On the other hand above that level market makers position on the gamma curve is positive in a positive gamma environment. Market makers have to trade against price to hedge their delta exposure. And that tends to subdue volatility. And for the first time in quite a while, SPX is trading below its volatility trigger in a negative gamma environment. And the next level up is the 4600 level. That is the absolute gamma strike. This is strike with the largest absolute gamma. And then finally, the 4650 level. And that is the call wall, the strike with the largest net positive gamma. And that can be expected to act as resistance. Alright, so those are the primary levels. Now let's take a look at a shorter time frames, timeframe still SPX. This is today in a one day one minute chart. I have the same levels on this chart. So SPX is trading below the lower weekly expected move and the lower daily expected move. Also trading below the volatility trigger. And then finally, here's the put wall down below. And that would be the next target for SPX, if it does continue lower. So those are the levels that are played for today. Alright, let's take a look at book map. Now book map, I have my cloud notes here.  So first of all, here's the spy 453 level. And that level did act as a point of consolidation this morning before price move lower. And then the 452 level also acted somewhat as consolidation before price move lower. And same for 451.  And that is the again, the strike with the largest net negative gamma and that did act as support almost to the tick for the ES S&P 500. Right. So those are the levels in play for today for the S&P 500. And note there were no shifts in levels overnight for SPX and spy. So the volatility trigger put walls, call walls and absolute gamma strikes for SPX and spy remain the same. And again, key levels really today have been the spy levels. And primarily the spy put wall at 450. Acting as support. And we'll talk more about setups in a few minutes. Alright, let's take a look at NASDAQ. All right, here's NASDAQ for the day. Down trend down below the QQQ valid put wall. Let's take a look at that in a QQQ chart. So here's QQQ for the day a one day one minute chart. The volatility trigger is at 381 up here. So QQQ is trading well below the volatility trigger in a negative gamma environment. Note the put wall at 375. It acted as support earlier, and then price broke below the put wall. And now is attempting to trade above. So very weak day for the NASDAQ today. And let me just point out, there's a considerable void below 375 the next level down is this 370 level next gamma level. And if price continued lower, that would be an obvious target for for QQQ. Alright, let's go back to book map. Now look at the NASDAQ futures and Q futures. And note the 380 level here, the QQQ 380 level. That is the absolute gamma strike for QQQ. Did act as resistance pre market. And again, here's the 375. And then here is the NDX 15,420 volatility trigger. So NASDAQ is trading below the NDX and the QQQ volatility triggers. And we'll take a look at setups in a few minutes. So pretty, pretty wide range in NASDAQ today about 300 points. So far from what I'm showing on this chart. Alright, there were just minor shifts and levels for the NASDAQ for NDX, the volatility trigger shifted slightly higher. And for QQQ, the volatility trigger shifted slightly lower. Otherwise, the put walls call walls and absolute gamma strikes all remain the same. And again, we'll take a look at setups in a few minutes. And take a look at what options traders were doing and see this in more, more detail. Alright, let's take a look and gamma notional to see how market makers were positioned at the beginning of the day. So at the beginning of the day, this is market makers gamma notional market makers position on the gamma curve for SPX, spy, NDX and QQQ. And really, it was fairly benign positioning at the beginning of the day, still positive for SPX, although less positive than yesterday. And then for spy minus 321, market makers position on the gamma curve shifted to negative for spy from slightly positive 14 yesterday to minus 322 today. And then for QQQ, gamma notional shifted more negative from minus 132 yesterday to minus 181 today. So overall, gamma notional shifted lower, either less positive or more negative. So less positive for SPX and more negative for spy and QQQ. And this leads me to a thesis of looking for a little bit more or higher volatility than yesterday. Now keep in mind, this is based on options positioning during the day yesterday. So this was all before the pitch downgrade came after the market closed and after the options markets closed. Alright, to get a sense of how market makers may react with the additional news, given their current gamma positioning, we can take a look at the Vanna model. I think it's very insightful today. So I'm going to take a look at the Vanna models for SPX, spy and QQQ. What this chart is showing is market makers delta notional and how that changes that's on the vertical axis and how that changes with price shown on the horizontal axis. So right now, SPX is trading right around 45 22. So that's right around here. So what this chart is showing, there are two curves on this chart. First of all, the gray curve is showing how market makers delta notional may change with changes in price only. And then the pink curve or purple curve is showing how market makers delta notional will change with changes in price and implied volatility. And that's the van effect, the change in delta with a change in implied volatility. And what this is showing is if price decreases, market makers will have significantly more delta notional to hedge as predicted by the price only the gray curve. Right, so let's go back and take a look at where SPX is right now. That's 45 22. So that is firmly in the negative gamma portion of this curve. So this is showing is if price decreases, really from around 4600 continues to decrease and apply volatility increases, market makers will need to sell futures to hedge their delta exposure. So this is typical again of a negative gamma environment where traders are long puts, market makers are short puts. And when price decreases and implied volatility increases, they have to sell futures to hedge their delta exposure. They want to remain delta neutral. So this works both ways. As price decreases, market makers have to continue to sell futures. So this gives us a good idea of the potential for a sharp move lower as price moves down to this portion of the Vana curve here. Then again, it works the two ways. If price increases, and implied volatility decreases, market makers can buy back their short futures. So this is why I say in a negative gamma environment, market makers have to trade with price, and that tends to enhance or increase volatility when market makers are trading in the direction of price. Alright, so that's the Vana model for SPX. We'll take a look at spy. Right now, spy is trading just above the put wall. So that's at 450. And again, remember, well below the volatility trigger at 456, and the negative gamma portion of the curve, same as SPX, and then finally for QQQ. QQQ is trading at three just below 375 just below the put wall. Let me zoom in on this. So this is the 375 level. So again, QQQ trading firmly in the negative gamma portion of this curve here. Again, so leading market makers have to trade with price to hedge their exposure. And that will that definitely enhanced the the move lower today, or contributed help to contribute to the move lower today. As price got going, remember the 380 level acted as so QQQ gap down 380 acted as resistance and price move lower down to 375. So that's why I always look at this gamma notional and the Vana model to get a sense of how market makers may react with changes in price and applied volatility and what what sort of trading range and volatility to expect for the day. So based on this, I was looking for a again higher volatility, more of a trend day and, you know, based on the the gap down this morning, certainly looking for a bearish move. Okay, so that was my positional analysis, reviewing the levels, the gamma notional and the Vana model. I developed a thesis. Alright, let's take a look at some setups now. So let's start with the SMB 500. I'm going to zoom in on this. So what this chart is showing is price for SPX with a white mine. And I've got two lines here. I'm looking at the hero signal hedging impact real time options for a combined signal for SPX spy, XSP and each ES futures all combined into one signal. And I have two lines here. The first purple line, the one that I typically show, that's for all expirations. That's for today, tomorrow, Friday, next month, all expirations. And then the green or teal line is showing just zero DTE. So that's what showing what the traders doing with options that expire at the end of the day today. And I'll talk about why I was looking at that in just a moment. So often the zero DTE traders are in the market fading moves. So they have in the past few months been providing a kind of a mean reverting price action. So they will buy dips and sell reps. And that has tend to tended to subdue volatility in the SAP 500. So when I was anticipating, I'm going to zoom in on the morning. And this was a question question I had of of with this move lower, how would the zero DTE traders react? So the initial reaction was as expected. And note the strong note how close the zero DTE line is to the all expirations, indicating that zero DTE options traders were driving a lot of the options water flow in the SAP 500 today. So this is what I expected. Right at the open, the zero DTE options trader started taking positive delta positions. And that led to a short bounce higher. They took their foot off the gas, and price started to move lower again. So that was around 935. And we'll take a look at this and book map and see exactly what happened in just a minute. Then that happened again, right around 1015 1017. Right here, they started taking positive delta positions again. SPX moved higher. Yes, moved higher. They took their foot off the gas, and price moved lower. So ultimately, these bounces higher were just setups for short increase. But we'll take a look at book map to and take a look at the signals in there. I think it's kind of interesting. Alright, so let's go to book map. Go back to zoom in on this Oh, first hour hour and a half in the morning. So what I was noting here with these red squares were the similarities between these two moves higher. Remember, zero DTE options traders taking positive delta positions, helping to move price higher. So when options traders do that, market makers have to in this case, buy back short futures. But that was short lived. But let me point out the similarities and these moves higher. So first of all, as prices moving lower, so we know that options traders are buying or taking positive delta positions, this small move higher in the iceberg line there, the light blue line shows traders larger traders buying on the way down with iceberg orders. Alright, the next thing to notice here is the the limit buy orders that come in there in the order book. And again, that was short lived right up to this liquidity at 4545 70 options traders take their foot off the gas, and price continues to move lower. Alright, here's a similar very similar setup. Again, remember, this was around 1015 1017 options traders, zero DTE options traders started taking positive delta positions. At the same time, large traders buying with iceberg orders. They used to hide their size. And note that traders tracing tracing chasing price higher with their limit orders, just like this setup, very similar setups. But that also failed as options traders took their foot off the gas, and price continued to move lower. So really interesting repeating patterns here. Again, ultimately just setting up entry points for short. Alright, let's take a look at NASDAQ. Let me zoom in here. We'll zoom in and then we'll see what options traders were doing. Alright, so let's go back to hero now. I'm going to turn off the zero DTE trades. We'll come back to look and look at the live market in a few minutes. So let's go take a look at NASDAQ now. So just like the SAP 500, this is a combined signal for NDX and QQQ shown here NASDAQ combined signal NDX and QQQ. So if you trade NASDAQ, this is a signal you want to take a look at. Let's zoom in. So one thing that I wanted to take a look at here is this move right around 937. This move higher lasted maybe less than 10 minutes. Options traders taking positive delta positions.  And then price continued lower. So let's go take a look at book map. So there's the this little cluster where that move with options traders just slowed price down. And then price started to make lower highs and then broke decisively lower just after 10am. So let's go back and take a look at hero. So overall, though, the trend of hero has been lower. And note, when hero, let me zoom in on this may be a little bit easier to see. Whoops. So hero moving slightly lower. And then when traders start taking negative delta positions more aggressively, price starts to drop as well. So definitely short setups in SPX, or yes, the SAP 500 and NASDAQ, a little bit easier to read for me and NASDAQ today. All right, any questions, any, any comments, questions? If not, we'll start taking a look at some stocks. Alright, let's take a look at some stocks. So what I want to do today is show an approach for finding stocks to trade. So we know that there was definitely negative or bearish news yesterday, market gap down. And a way to approach that is to rank either your watch list or the entire list of stocks that support hero here. So I clicked on my on this hero signal this morning, so that it ranks the stocks of my watch list from weakest to strongest hero signal. So what this hero signal is showing, and let me show AMD for an example. I talked about this with met on for bullish setup. Earlier this week. So what this is showing the dot is the current signal. And then this entire slider, I'm it's probably impossible to see but this entire slider is showing the range of the hero signal for the last 30 days. So the signal for AMD is the weakest, the lowest lowest that it has been in the last 30 days. And then the colored portion is showing the last five days. So AMD, the hero signal is the weakest that it has been in the last 30 days, and also weaker than it has been in the last five days. So let's just go through the signals with in this order. So first of all, here's QQQ. Very weak signal for NASDAQ. NASDAQ is definitely weak today. So we've already talked about that. This little bump up, bump up move lower, and then the sharp move lower, and price follows. And then the next is AMD. And remember AMD reported earnings after the close yesterday, they're last yesterday, there was an initial bullish reaction. But this approach of looking at stocks either in the watch list or the entire list of stocks, I think is a pretty solid approach for for looking for setups for the day. Right. So here's AMD, the entire day traders are selling calls and buying puts both these numbers are negative and calls really driving price action. And trade AMD traders were buying calls yesterday. When traders buy calls, market makers sell calls, and they have to buy stock to hedge their delta exposure. And now traders are selling calls, and market makers can sell their long stock edges. So that is definitely what's going on today. They're also buying puts that number is also negative. Both numbers negative, they're selling calls and buying puts. And let's look at some key levels here. 120 is the call wall key gamma strike price trading below that level. 112 is the hedge wall. And that slowed down price for a little bit. And then here's the 110 put wall that can be expected to act as support. Alright, let's go take a look at book map now. Let's go to AMD. And I'm going to zoom out and look at the look at the move from yesterday. So I've got I loaded 24 hours of data when I opened book map this morning. So this is the this is the cash open yesterday. Here's the close AMD close just below 118. Then here's the reaction. After reporting earnings, and that must have been just from the earnings numbers. And then there was appears to be a bearish reaction. I think that came after the must have come after the press conference. And then here's the reaction today, pre market trading higher just above the 120 call wall and key gamma strike. And then as soon as the cash open and options started trading, traders started taking negative delta positions that we just saw an hero and price moved down below the 120 level and continued pretty sharply lower, setting up a great short. So again, just ranking your watch list by hero signal gave a great clue to look for a short set up. So here's the 120 120 call wall price open below that level. Here's the 120 112 Hedgewall did act as a little bit of a consolidation point. 112 Hedgewall 110 put wall also acted as a point for consolidation. And then price continued lower down to the liquidity at 108. And now is attempting to make a recovery. Right? Let me check for questions. Alright trade and sale says your analysis and preparations are very similar to pre flight briefing and pre flight checks, as well as in flight checks, you must be a pilot very impressive. Thank you. You're very welcome. Thanks for your kind words. Alright, and you seen asked NASDAQ I've already covered NASDAQ today. So if you just came in, if you missed the analysis from earlier, this session is recorded. Just go to the bookmap YouTube channel and look in the archives. Later on this afternoon, you should see the recording where I cover NASDAQ earlier today. Alright, so super new be asked as the hero signal change noticeably before earnings. AMD had earnings yesterday. And you has earnings tonight. Curious if hero can reveal any clues on sentiment differences between the two stocks. Their charts look identical today. I don't know if you is available in hero. So we'll take a look at hero for yesterday. And notice, I as I recall yesterday, let me look at my notes that traders were buying calls yesterday. It's what I have in my notes yesterday. So we can take a look at hero and the hero signal should be rising for yesterday for AMD. So traders were buying calls. And it looks like they were. So that's why I said AMD traders buying calls market makers sell the calls. And they have to buy stock to edge their dealt exposure. And as AMD is dropping today, traders are selling the calls, and market makers can sell their long stock edges. So when I get through with the other stocks I want to take a look at we'll take a look at you. And then we can take a look at the hero signal for AMD yesterday. Alright, so great shirt set up in AMD. Now let's go back to hero go to the next stock I want to take a look at. So we're going to work down the list here. And the reason I'm ignoring the S&P 500 ES futures, we've already looked at the combined signal for the S&P 500, which combines SPX spy and ES. And by the way, the the ES futures traders for S&P 500 got it right. Much more so than the SPX traders and the spy traders. Alright, so the next stock in the list is Google. So of the stocks in this list, the next weakest signal, let me zoom in. In this, there was a divergent setup. What I'm looking at is the hero signal moves lower. A few minutes, maybe just about five minutes before price and price reverses at the 130 level, setting up a nice divergent short. Let's go take a look at Google and book map. So here's the reversal at 130. The 130 level, as traders started taking negative delta positions and price move lower, looks down a couple of points. Google's not a big mover. But a hero signal has worked pretty well for Google recently. So nice reversal at 130 as traders started taking negative delta positions. Let's take a look at Nvidia and Karma FX. Thank you for your kind words. Alright, it looks like I need to need to move down the levels on Nvidia. So I've just got to update my spreadsheet. Anyway, let's take a look at we'll focus on the move this morning. So let's go take a look at Hero for Nvidia. Actually, Microsoft was next on the list. We'll take a look at Microsoft. Sorry, I skipped over that. So Microsoft traders taking negative delta positions. Let's go to Microsoft. Then we'll get back to Nvidia. Alright, so another great short setup for Microsoft. Hero signal pointing the way pullbacks and if price had started to move continue to move lower, 325 would be the next target. So notice the high liquidity at the big round numbers, the zeros in the fives. That was the first first price price target 330, then 329, 328, 328. Let's go back and take a look at Hero. Microsoft traders were selling calls and buying puts just like AMD and 325 that area with high liquidity is the put wall for Microsoft. Let's go to back to Nvidia now. I'm going to skip over IWM. I don't have that in book map. Back to Nvidia 45750 is the hedge wall. And that's around the point where price moved lower right here. 445 the put wall. Let's go to book map go back to Nvidia. So 45750 right around here, the hedge wall price moved lower. 445 the put wall had very little impact. That's pretty typical of volatile stocks like this put walls and call walls don't necessarily act as support and resistance like they do for the SAP 500 and again, in volatile stocks like like Nvidia. So it looks like the 435 level did finally act as support. You can see all of the aggressive buyers finally come in note the shift from pink dots market sell orders to market buy orders shown by the green dots. Let's see what options traders are doing now. So options traders started taking positive delta positions right around 1215. And then price responded a few minutes later about 15 minutes later, started moving higher. So that's at the 435 level. Let's just take a look at something else. Get a sense of the option structure at that level. So let's go to so here's the 435 strike note there is more put gamma that's shown by the blue bar below the zero line and call gamma. And one interesting thing to note here is this, these aren't the orange and blue line. So the blue line is showing put notional gamma. And the orange line is showing call notional gamma. So below around around 475, just above the key gamma strike, put notional gamma starts to starts to dominate and note also that these lines start to level off. The call line really definitely starts to level off. Let's go back to our current level right here. Actually both levels, they start to level off around this level that these they're less steep. steeper here indicates more volatility. And as these lines level off, this indicates that market makers are fully hedged, they may not have any additional hedging to do. And if you're looking for a low point, and like a, you know, potential bottom in a stock, that's a good point to look for is this point where these lines really start to level off. Indicating again, market makers are fully hedged, and may not have any additional hedging to do or much may not have much additional hedging to do. And again, if you're looking for a longer term entry point that that would be something to consider. So that that could be what is what is happening with NVIDIA and why traders are coming in at that point. So we know that the levels, the volatility indicated by the these sloping lines here that's leveling off, indicating market makers are fully hedged, we know that traders were taking started taking positive delta positions. And also aggressive buyers were coming in right around that 435 level. Let's go back to book map. Really strong signal here with with the order flow. Let's zoom in on that. You can see the the final cell sweep that shown by these bright red dots, small bright red dots as aggressive buyers start to come in. This is showing absorption here this these blue numbers and aggressive buyers, of course, coming in. It takes them a while about 15 minutes to turn price around as options traders are taking positive delta positions. Alright, so that's NVIDIA still moving higher. Let's take a quick look at Tesla. Tesla was kind of doing its own thing today. Finally started to move lower, but initially moved higher. And note all the green dots here aggressive buyers coming in, kind of a deep pull back almost to 255 and aggressive buyers come in again. And then finally, and Tesla gives in to the move lower. Let's take a look at cumulative volume delta for Tesla. And I normally don't look at cumulative volume delta for stocks, but it often gives a pretty good signal for Tesla. And here you can see the the shift in order flow aggressive buyers. And then aggressive sellers start to come in. Price moves lower. And then CVD shifts higher. And you can see the change in order flow here. The aggressive buyers start to come in. Price moves down another point or so makes a higher high, another higher high. And now it's continuing higher. Let's see what options traders were doing. And then we'll take a look at you. Alright, so let's go take a look at Tesla. And note if we scroll down the list, Tesla is toward the middle of this list. Not really a strong signal or a weak signal here in the watch list. It's shown being positive or strong. So note the for Tesla for the net net for the day, no snow value is positive. And there's a strong correlation between hedging flow and price action with Tesla today. Price moves up as traders were taking positive delta positions. Price moves lower, setting up that higher low for another move up before cumulative volume delta and options traders finally shift lower until about the same time 12 10 12 15 that and Nvidia reversed higher. Tesla did the same thing. So a little bit different tone for Tesla today. Positive delta positions overall. So traders are buying calls. Orange numbers positive, they are buying puts, but call buyers are more aggressive. Alright, let's take a look and see if you is in here. I'm not sure, not even sure what that is. And sorry, super newbie, I don't see that. Alright, so again, sorry, let's go back to AMD. And what I can do here in AMD is take a look at yesterday so we can compare yesterday to today. So I'm going to change the date to Tuesday. So we'll just look at Tuesday in isolation. So this is looking at yesterday for AMD. And traders were buying calls and selling puts yesterday. The rising orange line shown traders are buying calls. And then these they were selling puts as well. But the call buyers are definitely more aggressive. Both numbers are positive. So that's yesterday. Let's go back to today now. This one first. So hero provides up to five days of a look back. Alright, so karma FX asked about Palantir, Amazon, and AI. So I believe all those stocks are in here. So we'll start with Palantir. And I sorry, I don't have I don't have Palantir and book map or AI or Baba. Alright, so here's Palantir, strong correlation between options trades hedging flow and price action. Traders selling calls. They're also selling puts selling volatility today but call call sellers more aggressive. Alright, there's Palantir. We'll take a look at AI next. C three AI. Same thing. Traders are buying puts and selling calls. Let's go to Baba. Same thing. Traders selling calls and buying puts both are negative. Price moving lower. Attempts to recover around 1215 just like most other stocks.  Let's take a look at the total signal. Amazon trading below the 130 key gamma strike. Looks like that was resistance this morning. And the 128 hedgewall did act as support initially and then price broke below that level. Took a little bit longer for Amazon to reverse higher. Note this large block trade here. That's what the vertical line indicates. Let's see what traders are doing. So traders were buying calls today. After this large block trade. Right around 950 traders some traders selling calls and then right after that. So large institutional trade selling calls and then other traders start to come in and buy calls. Notional value for calls is positive. And also now notional value for puts is positive as well. Indicating net traders are selling puts. It's indicated by this large block order they're selling puts. Alright, we'll go to book map and then wrap it up. Go to Amazon. So Amazon 130 I believe that was the key gamma strike. Let's just go back. Yeah, 130 the key gamma strike price opens that level and moves lower. And that starts to reverse higher. Traders started taking positive delta positions. Right around 1230. A little bit later than some of the other stocks we looked at. Alright, so the SMB 500 still trading above the spy 450 put wall, but not much higher. Alright, so trade and sale ask. Maybe we look at a hero as a kind of leading indicator. And if so in stocks or indices or futures. So I look at hero in two ways. As a leading indicator or as a confirmation. And I want generally I want to be on the side of market makers. So if traders are taking negative delta positions, market makers either have to sell stock or sell futures to hedge their delta exposure. I want to be on the same side as that. And then on the other hand, if traders are taking positive delta positions, market makers have to buy futures or buy stock to hedge their delta exposure. Now regarding the question about leading indicator, that happens more often in indices. So I look for that setup often in the especially the SMB 500. Looking for a leading indicator. There are a lot of a lot of players a lot of different influences on the SMB 500. And sometime there can be a little bit of a lag effect. So I think that may be why the hero indicator can act as a leading indicator for price. So one of my favorite setups is for, let's say prices moving higher to a potential resistance level. And traders start taking negative delta positions as prices moving up to that resistance level. So I'm looking for a reversal lower at that resistance level. And I look for looking book map for confirmation in order flow. But on the other hand in stocks, hero is typically a just a confirmation. Right? So I hope that helps. Karma FX, you're welcome. Again, thank you for your kind words. I'm a little bit over my time today. I hope I answered everyone's questions. Thank you very much for watching. Thanks for your questions and comments. And let's see if we have anything coming up tomorrow. Oh, Apple and let's see Apple, Apple and Amazon report after the close tomorrow, jobless claims in the morning services PMI. And then on Friday, the employment report. So we will will prepare for the Apple and Amazon earnings tomorrow afternoon. So again, thank you very much. Thanks for watching. Thanks for your questions and comments. And I will see you tomorrow. Thanks again. Bye


Okay are you ever looking for a power strip you can use outside? This one is the CLN power strips waterproof. Okay 45 degree flat plug IPX6 waterproof 360 swivel cord and it's got three AC outlets so it's only got three outlets on it. It's waterproof like I said overload protection switch. High-level waterproof it can be used indoor and outdoor where water is easy to splash such as kitchen, bathrooms from equal area, terrace.  It comes in black and white the cable length is six and a half feet six point six feet. High quality brushed panel forbidden to use in thunder and lightning. Don't support it you can't immerse it in the water it's not you can't drop it in a bucket of water. Don't use it under load. It may need a little more force to insert due to the shock proof outlet design rubber cover switch for extra dirt. So you might have you might have to force the plug in it might be hard to plug in because it's it's waterproof so it's a tight fit all right. So this is the white one. That's what they mean by swivel it comes it moves all the way around okay. So you can turn it in in direction you want to turn it into that's a pretty cool little item all right and got all your things on it mounting on the wall you got your little screw things on the back it's got your arm off switch there and pretty heavy duty waterproof little design. I'm going to take it out and check it out. I what I'm going to use this for is out on the deck we have a tv out on the deck and we have you know something outdoor lights that we have around the deck and I'm going to use this right now I have a power, a regular power strip out there but we always unplug everything because we're afraid of rain. This one now it's waterproof we're going to leave it out there and I'll see what it looks like when it's done.


It's crazy when you think about all the different kinds of foods we eat. We just swallow and hope it all works out for the best. Well, it turns out there are better ways to think about keeping our bodies humming healthfully along. Welcome to Nutrition Facts, I'm your host, Dr. Michael Greger. Today, we take our recently decluttered living spaces and try to clean them without passing out from the harsh chemicals. And yes, we're talking about cleaning products, so what do we use? Here's our first story. Household cleaning products can be hazardous, landing hundreds of thousands of children in U.S. emergency rooms, and the product most commonly associated with injury was bleach, which can be toxic, even if used as directed. We've known that those with asthma who work with cleaning products day in and day out can suffer adverse respiratory effects, over worsening of symptoms, declining lung function, and inflamed airways, but even cleaning workers without asthma can be affected. Even below so-called acceptable exposure levels, cleaners with or without reactive airways can suffer a substantial decrease in lung function. OK, but that's people who clean for a living. Although we've known that occupational use of bleach may have adverse respiratory health effects, it was unknown whether just common domestic use of bleach in the household may put lungs at risk until now. Bleach use was significantly associated with nearly five times the odds of non-allergic adult onset asthma, as well as ongoing lower respiratory symptoms such as chronic cough. The way bleach works is as such a strong pro-oxidant that the thought is that it can lead to leaky lungs and allow allergens to penetrate. This phenomenon of cleaning product-induced asthma has been known for decades. More than three-quarters of the dozens of population studies looking into it have found increased risk of asthma or nasal inflammation. Ideally, safer cleaning products should be available. Unfortunately, this body of evidence has been largely ignored by the manufacturers and commercial cleaning companies, and most of workers put at risk are women. In fact, that may help explain some of the gender differences in asthma. The relatively high frequency of bleach use for home cleaning by women around the world, together with a strong association between bleach use and non-allergic asthma, emphasizes the need for reconsidering the use of bleach for cleaning. There are natural, environmentally friendly cleaning products that may offer a safer alternative, safer, perhaps, but are they as effective? We didn't know until now. The effectiveness of three home products in cleaning and disinfection of Staphylococcus aureus, the bacteria that causes staph infections, and E. coli on home environmental surfaces. The first report ever of the performance of a purportedly safer alternative. In the home setting, some individuals will select conventional products such as bleach due to familiarity, it's a smell some associate with cleanliness. They are seeking less hazardous and environmentally preferable green, organic, or natural disinfectants, which you can buy or make yourself, so-called DIY do-it-yourself recipes that typically involve ingredients like vinegar, clup soda, and plant essential oils such as tea tree oil prized for its antimicrobial qualities. So researchers pitted head-to-head chlorox bleach versus a natural disinfectant based on thymol, which is from thyme essential oil, versus a DIY recipe, half clup soda, half white vinegar with a few drops of tea tree oil. You could probably buy the bleach for around three bucks, the natural stuff from like $7, but the DIY mix for less than a dollar. Yeah, but does it work? On the bottle, it says bleach can kill 99.9% of germs, which is the EPA standard for the disinfection of surfaces that don't come into contact with food, like the bathroom sink or something. They claim 99% of germs, but when put to the test, the bleach actually killed 99.999% of germs, completely wiping out the E. coli and staff germs, which even exceeds the EPA standard for food contact surfaces like the kitchen counter, and so did the expensive natural stuff. Worked just as well as the bleach. But the clup soda vinegar tea tree oil concoction flopped, allowing as many as a few percent of the staff bugs to thrive. Now maybe they didn't use enough of the tea tree oil, only adding about a drop per cup, but from a performance perspective, the environmentally preferable product is an effective alternative to conventional bleach, and I would say even better since bleach is well known as a respiratory irritant, and it's corrosive too and manned up damaging surfaces. What I would find interesting is to test how effective a cheap DIY time oil solution would be. In our next story, we find the reasons the Centers for Disease Control and Prevention prohibit not only smoking, but also scented or fragranced products in their building. In a recent review of the damaging effects of household cleaning products on the lungs, researchers noted that the adverse respiratory effects of cleaning products were first observed in populations experiencing high levels of exposure at the workplace, such as cleaners and health care workers, with a primary focus on asthma, but the occupational use of disinfectants has also been linked to a higher risk of developing chronic obstructive pulmonary diseases like emphysema. And now we know it's not just workplace exposures, but also common household exposures that are risk factors for respiratory disorders and childhood, as well potentially an important risk factor for adult asthma, with common household cleaning spray use accounting for as many as 1 in 7 adult asthma cases. The thought is that the inhalation of chemical irritants may cause injury of the airways that leads to oxidative stress and inflammation. OK, so what can we do about it? Well, it may indeed be limited to sprays. Cleaning products not applied in spray form were not associated with asthma, and it's possible that environmentally friendly cleaning products may represent a safer alternative, though they may still present some risk. Ideally, safer cleaning products should be available. Unfortunately, the research suggesting harm has seldom been heated by manufacturers, vendors, and commercial cleaning companies. I wonder how much of that is because most of the workers exposed to cleaning products, both occupationally and presumably domestically, are women. One of the problems may be the fragrance chemicals. One in three Americans surveyed reported health problems, such as migraine headaches and respiratory difficulties, when exposed to fragranced products. And in about half, it was so bad they actually lost work over it. Results from this study reveal that more than one third of Americans suffer adverse health effects, such as respiratory difficulties and migraine headaches, from exposure to fragrance products. Of all individuals, half reported that the effects can be disabling, yet more than 99% of Americans are exposed to fragrance products, at least once a week. The effect on asthmatics may be even worse, affecting closer to two thirds. One compound that may be of particular concern is called 1,4-dichlorobenzene, also known as para-dichlorobenzene, which is found in many air fresheners, toilet bowl deodorants, and moth balls. It breaks down in the body into a compound called 2,5-dichlorofenol, which you pee out, giving researchers a reliable measure of your dichlorobenzene exposure. Not only may it make respiratory problems worse for those already suffering from compromised airways, but exposure to dichlorobenzene at blood levels found in the general US population may result in reduced lung function in people who start out with normal breathing. What's worse, higher exposure was associated with greater prevalence of cardiovascular disease and cancer. That's not good, so better read the labels, right? Surprisingly, there is no law in the US that requires the disclosure of all ingredients in fragrance consumer products. In fact, for air fresheners, laundry supplies, and cleaning products, they don't even need to say it has fragrance at all. You don't know until you smell it. So if you can't tell which products have which chemicals, you can follow the lead of the CDC, the Centers for Disease Control and Prevention. Not only is cigarette smoking indoors prohibited at all times, scented or fragrance products are also prohibited at all times in all interior space, owned, rented, or leased by the CDC. I wish rideshare services like Uber and Lyft would have a similar policy or at least a fragrance-free option. But one in five of more than 1,000 American surveyed said they would turn right around and leave a business. They smelled air fresheners or some fragrance product, so it's in business's best interest too, since more than 50% of the population would prefer that workplaces, healthcare facilities, and their healthcare professionals, hotels, and airplanes were fragrance-free. Finally today, we learn how vault of chemicals in consumer products such as air fresheners, laundry detergents, fabric softeners, and dryer sheets may be hazardous. In addition to meat, exposure to common household chemicals may exacerbate or induce allergies, asthma, and eczema. Researchers at Harvard and all around the world collected air samples from where children slept and demonstrated for the first time that the bedroom concentration of propylene glycol and glycol ethers was significantly associated with an elevated risk of multiple allergic symptoms, runny nose, and eczema. This class of chemical compounds is found in cleaning fluids, pain, pesticides, PVC pipes, varnishes, and may be one of the reasons we've seen an increase in these kinds of diseases around the world over the last few decades. Recently, researchers put a few consumer products to the test. Air fresheners, laundry detergents, fabric softeners, dryer sheets, each with annual sales over $100 million. Six products, nearly 100 volatile chemicals, identified, though none were listed on the labels, usually just says something like fragrance. And 10 of the chemicals they found are regulated as toxic or hazardous, with three officially classified as hazardous air pollutants. For example, the fabric softener they tested. On the label it just says biodegradable fabric softening agents. And it even smells like mom when she leans in for a good night kiss. But this is what they really found, including the carcinogenic hazardous air pollutant acetyldehyde. What about if you just stick to the naturally scented products? Even products advertised as green, natural, organic, emitted as many hazardous chemicals as standard ones. For example, a soap boasting pure essential oils and organic tea infusions also contained all of these. Yeah, but what if you somehow know for certain it's all just natural, like the limonene? That's a real phytochemical found in real citrus. Until it photo oxidized with ozone and ambient air to form dangerous secondary pollutants, including formaldehyde. When it comes to consumer products, the best smell is no smell. We would love it if you could share with us your stories about reinventing your health through evidence-based nutrition. Go to nutritionfacts.org slash testimonials. We may share it on our social media to help inspire others. To see any graphs, charts, graphics, images, or studies mentioned here, please go to the Nutrition Facts podcast landing page. There you'll find all the detailed information you need, plus links to all the sources we cite for each of these topics. For our timely text on the pathogens that cause pandemics, you can order the e-book out of your book or hard copy of my latest book, How to Survive a Pandemic. For recipes, check out my new How Not to Diet Cookbook. It's beautifully designed with more than 100 recipes for delicious and nutritious meals. And all the proceeds I receive from the sales of all my books goes to charity. NutritionFacts.org itself is a non-profit, science-based public service where you can sign up for free daily updates on the latest in nutrition research via bite-sized videos and articles. Everything on the website is free. There's no ads, no corporate sponsorship. It's strictly non-commercial. I'm not selling anything. I just put it up as a public service as the labor of love as a tribute to my grandmother, whose own life was saved with evidence-based nutrition.