Todd:Chem3x11 ToddL13

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Chem3x11 Lecture 13

Incomplete Friday Jun 1

This last lecture is about two other classes of pericyclic reactions, namely cycloadditions and sigmatropic rearrangements.

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Key concepts

  • Cycloadditions and sigmatropic rearrangements are governed by similar orbital considerations to those we've already seen


Cycloadditions are pericyclic reactions where two components come together to give a cyclic compounds. The best-known example is the Diels-Alder reaction. The reaction occurs between a diene (with 4 π electrons) and a dienophile (with 2 π electrons); we talk of this reaction being a [4 + 2] cycloaddition. Three π bonds and a σ bond in the starting materials become one π bond and five σ bonds in the product.

Scheme 1: Typical Diels-Alder Reactions

Again, there are no intermediates, just a cyclic transition state. The stereochemistry of the starting materials is carried through to the products, as can be seen by the above example. We need to explain why this is, as well as explaining other things about the reaction.

General Orbital Requirements for a Diels-Alder Reaction

As for electrocyclic processes, the lobes of the MOs on the interacting atoms need to be in phase. We should look at the frontier orbitals of the two reagents. Looking at the diene and dienophile drawn on paper, it's not clear which interaction is most energetically likely, but it turns out the HOMO of the diene interacts with the LUMO of the dienophile. (The other interaction is symmetry-allowed, but the orbitals are often quite far apart in energy and do not dominate the interaction unless the electronics of the reagents are unusual, giving what are called "inverse electron demand Diels-Alder reactions" which we don't cover.)

Scheme 2: General Diels-Alder Orbital Reactions

You'll notice that the two components approach and interact using MO lobes that are on the same face of each. i.e. the diene uses two lobes on one face and the dienophile uses two lobes on one face. This is a suprafacial-suprafacial interaction. The interaction between diene and dienophile is very sensitive to what's attached to the different systems. The simplest DA reaction on paper is very hard to get to go, but small steric and electronic changes to the structures of the reagents means the reaction can go very quickly.

Scheme 3: Influence of Reagent Structure on the Ease of a DA Reaction

The activation of the dienophile in the case above is electronic in origin. If we are to promote a cycloaddition, we need the frontier orbitals (of the right symmetry) to be close in energy - that provide the greatest energetic benefit when the new bonds are formed.

Scheme 4: Orbitals Close in Energy Produce the Greatest Energetic Benefit from the Interaction

Usually a DA reaction employs an electron-rich diene. If it's electron-rich, it has a high energy HOMO. It thus helps if we have a low energy LUMO to go along with this HOMO, and we can achieve that by making the dienophile electron poor. The simplest way to do that is attach a group that is electron-withdrawing to the π system, for example a conjugated carbonyl group. Obviously the interacting orbitals are the ones shown here, and this diagram should bring some questions to your mind about the three-dimensional nature of this interaction, which is the cool thing we'll get to in a moment.

Scheme 5: The Interacting Orbitals of the DA Reaction in Scheme 3

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