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Ch. 1 - A Review of General Chemistry
Ch. 2 - Molecular Representations
Ch. 3 - Acids and Bases
Ch. 4 - Alkanes and Cycloalkanes
Ch. 5 - Chirality
Ch. 6 - Thermodynamics and Kinetics
Ch. 7 - Substitution Reactions
Ch. 8 - Elimination Reactions
Ch. 9 - Alkenes and Alkynes
Ch. 10 - Addition Reactions
Ch. 11 - Radical Reactions
Ch. 12 - Alcohols, Ethers, Epoxides and Thiols
Ch. 13 - Alcohols and Carbonyl Compounds
Ch. 14 - Synthetic Techniques
Ch. 15 - Analytical Techniques: IR, NMR, Mass Spect
Ch. 16 - Conjugated Systems
Ch. 17 - Aromaticity
Ch. 18 - Reactions of Aromatics: EAS and Beyond
Ch. 19 - Aldehydes and Ketones: Nucleophilic Addition
Ch. 20 - Carboxylic Acid Derivatives: NAS
Ch. 21 - Enolate Chemistry: Reactions at the Alpha-Carbon
Ch. 22 - Condensation Chemistry
Ch. 23 - Amines
Ch. 24 - Carbohydrates
Ch. 25 - Phenols
Ch. 26 - Amino Acids, Peptides, and Proteins
Ch. 26 - Transition Metals
Conjugation Chemistry
Stability of Conjugated Intermediates
Allylic Halogenation
Conjugated Hydrohalogenation (1,2 vs 1,4 addition)
Diels-Alder Reaction
Diels-Alder Forming Bridged Products
Diels-Alder Retrosynthesis
Molecular Orbital Theory
Drawing Atomic Orbitals
Drawing Molecular Orbitals
Orbital Diagram: 3-atoms- Allylic Ions
Orbital Diagram: 4-atoms- 1,3-butadiene
Orbital Diagram: 5-atoms- Allylic Ions
Orbital Diagram: 6-atoms- 1,3,5-hexatriene
Orbital Diagram: Excited States
Pericyclic Reaction
Thermal Cycloaddition Reactions
Photochemical Cycloaddition Reactions
Thermal Electrocyclic Reactions
Photochemical Electrocyclic Reactions
Cumulative Electrocyclic Problems
Sigmatropic Rearrangement
Cope Rearrangement
Claisen Rearrangement
Additional Guides

Thermal Electrocyclic reactions are pericyclic reactions in which 1 pi bond is destroyed after a heat-catalyzed cyclic mechanism.

Concept #1: MO Theory of Thermal Electrocyclics


Now it's time to learn about a new type of pericyclic reaction called thermal electrocyclic reactions. So, guys thermal electrocyclic reactions are just going to be pericyclic reactions in which 1 pi bond is destroyed and that's because any electrocyclic reaction is going to involve a 1 pi bond changing from the reactants to the products and that happens through a heat-activated cyclic mechanism because we know that it's thermal. So, it's going to be heat activated, cool? So, what do we need to know about this reaction? Well, one thing that you should keep in mind is that this reaction is always intramolecular. So, it's not going to involve two different molecules, it's just going to be one molecule reacting with itself in a cyclic mechanism to make a new ring, okay? It's usually a ring forming reaction and notice that, what would happen here is that we would start off in this specific example we're starting up with 3 pi bonds in the reactant and then after heat is applied, we end up with 2 pi bonds. So, this just goes ahead and it verifies that this is electrocyclic because remember that in an electrocyclic reaction you're always going to lose 1 pi bond, okay? Or 1 pi bond is going to change from the reactants to the products, cool? Also notice that here we're applying heat. Now, I do want to quickly go over the mechanism really quick and to show you guys what would happen. So, what would happen is that it's concerted and cyclic. So, it's all going to happen at the same time, you don't really need to know where to start or end from, but what we do need to know is that like we need to make that new single bond, right? So, what the way I would start it is I would take the electrons from this double bond and make a new single bond and then that means that this needs to break and put its electrons there, which means that this one needs to break and push its electrons there and there you have it, you would have your new ring and now we're missing pi bond, okay? So, guys it turns out that all conjugated polyenes are capable of doing these intramolecular electrocyclic reactions. So, it's not like a specific type, that's possible this could happen with any polyene however many pi bonds long, it could happen, however is that the stereochemistry is variable, meaning that you're not always going to get the same exact product, many times you can immediately predict, what ring you're going to get but to know where the substituents are going to be, we need to think one level deeper and we're going to have to think about frontier molecular orbital theory, right? We're going to need to think about HOMO and LUMO orbitals and figure out how that plays into this, so how do you determine the stereochemistry of the product? the way you do it is by looking at the HOMO orbital of the molecule, okay? And it turns out that the HOMO orbital is capable of cyclizing in one of two ways either in a conrotatory direction, okay? A conrotatory direction or in a disrotatory direction, okay? So, when we look at electrocyclic reactions, we're going to be looking at intra molecular reactions and we're going to try to figure out, did this molecule, did the molecular orbital have to rotate a conrotatory or disrotatory in order to form a new single bond and I know I just kind of did some hand motions but here I'm going to show you exactly what I mean, I have some examples drawn out for you already. So, to make a new single bond we're going to need two of the same face lobes to overlap, okay? So, what that means is that if we're trying to make a new bond, let's say with this 2, with this 4 pi system this 4 pi conjugated system here that I have on the left, what I would need is I would need like, for example, the positive here to overlap with the positive here, okay. Notice that they're on opposite sides though, so the only way that can happen is this both orbitals are obtaining conrotatory. So, what that means is that this one's rotating to the right and this one is also rotating to the right, okay? Because they both rotate the same direction, what's going to end up happening is that the positives are going to overlap, does that make sense? that's what conrotatory means that you're, it's kind of like they're rotating the same direction but what's actually happening is that you're bringing two opposites together, okay? So, orbitals rotate the same direction is conrotatory but what about a 6 pi system or 3 double bond system, if we were to try to make a ring out of this one, which is actually the example that we had at the top, that would actually be an example of this rotatory because in that case, when you draw the HOMO orbital, what you end up finding is that your orbitals are perfectly symmetric on both sides of the terminal ends. So, if you rotate conrotatory they're actually going to get the opposites interacting. So, this rotatory rotation happens when they rotate in opposite directions, one is clockwise and one is counterclockwise to create that same type of overlap that would lead to a single bond, okay? Now, why is this important, it sounds like no matter what we can get an electrocyclic reaction to happen thermal, no matter what if these are going to rotate conrotatory or disrotatory, but what matters is the substituents because if you have any substituents located on the terminal ends, let's say here or here, let's say that I put an alcohol here, right? how do you know if that alcohol is going to face up or down after the new mechanism is taking place? Well, that's why you have to look at the rotation type, the only way you can predict it is to know the rotation type, so the focus of our electrocyclic problems is not actually going to be on forming the ring because that's the easy part, we're always going to assume that the ring conform the focus is going to be on the stereochemistry because if you can predict the stereochemistry accurately that means you understand the molecular orbital rotation that's occurring okay? So, in the next video we're going to do an example including stereochemistry.

  • Always intramolecular

Example #1: Predicting Electrocyclic Products


Predict the product in the following electrocyclic reaction, label the reaction as either conrotatory or disrotatory. So, guys I just want to emphasize here that we know a reaction is going to take place no matter what, we know that we're going to get a mechanism that looks something like this, where, let's say this dual bond makes a single bond here and then this double bond goes here. So, what we're going to expect to get is some kind of square, right? With a double bond here and with methyl groups here, does that make sense so far? because we're making a new single bond here, but what is the stereochemistry of these methyl groups? are they cysts are they trans you can't just draw this and get the right answer, we have to actually provide the stereochemistry, the whole project not just ignoring stereochemistry. So, to figure out if these are facing up or down, we're going to have to look at the molecular orbitals. So, where do I think is a good place to start, we're starting from scratch here, what do you think we should do first? So, probably a good place to start is let's start drawing our molecular orbitals of a diene, so that means I have to draw four of four, right? a grid of 4 of 4. So, 1, 2, 3, 4 it's not bad, I'm going to use my copy-paste feature and you guys can always pause the video, if you need to. Cool. Awesome. So, now we can go ahead and draw in our molecular orbital names. So, we know, this is psi 1, psi 2, psi 3 and psi 4 and then we can shade these in, you guys should be pretty good at shading in dienes by now, why don't we just do this very quickly, it would be that all the bottom is filled, it would be that there's one node on the second one. So, then this is what it looks like because there's one node and the last one has to flip, for 3 and 4, the first one doesn't change, for 3 and 4 the back one keeps flipping then this would go down and then this would go up, cool? And then finally, we need two nodes and three nodes, that means that these two go up here and then this one goes up and down, cool? So, those are our Mo's, we should then fill in with the number of pi electrons we have, which is 4, cool? Awesome. So, now what do we do, what's the next step, this was important, we did need to do this but what's the next step, guys, we need to analyze the HOMO. So, remember that we learned in frontier molecular orbital theory, we learn about HOMO and LUMO and they learn how to identify both? Well, it turns out that we don't need to worry about the LUMO for electrocyclic, electrocyclic only focuses on the HOMO because it's just the HOMO interacting with itself. So, that's a good thing, if the in terms of the frontier orbital, there's less to worry about it's just the HOMO, so the HOMO happens to be this orbital here and this is the one that we have to figure out if it's going to be conrotatory or disrotatory, okay?

Now, the way that we tend, that we typically do, this is to actually try to do it in 3d. So, we can figure out, what it's going to look like at the end. So, what I'm going to try to do is I'm going to try to draw it like this with the orbitals facing up. So, we can see how they interact with each other, okay? Something like that. So, let's go ahead and draw in our orbitals, we're going to draw 1, 2, 3, 4, does that make sense? So, what I'm trying to do is I'm trying to actually keep it similar to that one but now I'm going to be involving what we know about these orbitals here, let's go ahead and shape them in, let's say that on this psi right here, it's the beginning of my LUMO on the other side, so that means that what it would look like is shade the bottom, shade the bottom, shade the top and shape the top, cool? Awesome. Now, don't forget, we have our substituents that we need to include. So, where are our substituents going? Well, they should go on the inside. So, that means is that I'm going to draw these as methyls, I should draw a substituent going in here and a substituent going in here, does that make sense so far? this has to do with these methyl groups right here, and this is how we're going to determine the stereochemistry. Awesome guys. So, now we have to determine, if it's going to be conrotatory or disrotatory, what do you guys think? so it should actually be conrotatory, right? Because notice that my lobes are in opposite ends. So, what that means is they both have to rotate the same direction that means this one, let's say it has to rotate clockwise, this one also needs to rotate clockwise or if you pick counterclockwise they should both rotate counterclockwise. So, what that means for my product is that what it's actually going to look like is like this. So, I have my, let's try to draw this in 3d still, in three dimensions. So, I have my new square my new cyclobutane, I know that I'm going to form a double bond here and then we have to look at with this rotation where would these groups go, where would the methyl groups go. So, what I would see is that, let's start off with the first one, the first one at the bottom, it was a, it's going into the page but after I rotate it it's going to rotate down, right? It's going to go down because of the fact that, that thing is rotating clockwise, the way that I drew it it's rotating clockwise. So, that mean it's going to rotate down. So, I would expect this methyl group to go down like this, I hope that's making sense so far. Now, the other one, that's facing this way, that's actually coming out of the page like, in fact, one way to write this could be that you would write this one into the page and this one out of the page because one is going into the page, one is going out of the page, right? So, then that one when it rotates it's actually going to face up, right? Because it's rotating clockwise then this methyl group would go up, which means that my product is actually going to be a trans dimethyl, where this one faces up and this one faces down. Now, guys it turns out that this is actually in enantiomer, this is not a meso compound. So, we should actually draw the other enantiomer as well, meaning that we actually get two products for this reaction, we get the two different trans pop products that are possible, which is this one and this one and you might be saying, we'll Johnny how would you get the other one? that would be if you had rotated counterclockwise then you would get the other one, cool? Awesome guys. So, I guess now we just have to label it and the rotation turned out to be conrotatory, cool? So, guys we did it, great job, we got our products, just so you know, it's not always going to be two products, if they had been facing the same direction that would then maybe a meso compound because it has a plane of symmetry and then you just get one product but since there was a symmetry here we had to draw both products as our answer. So, remember guys, when you're drawing electrocyclic you can't just draw them on the plane, you need to include stereochemistry because that's really, what your professor, what your homework is going to care about, making the ring is the easy part, the hard part is using HOMO-LUMO frontier orbitals to figure out the stereochemistry, great job, let's move on to the next video.