Sigmatropic Rearrangement

Microwave Signatropic Rearrangement Sigmatropic RearrangementThe first really interesting reaction seen by Organic Chemistry students is the Diels-Alder [4+2] cycloaddition, an example of a concerted process where all the bond making and breaking take place concomitantly. The SN2 is also a concerted process, however the Diels-Alder reaction is a gem because of the high density of relative stereochemistry that can be established in a single synthetic step. The most interesting and unique of all organic reactions learned fall within the narrow category of sigmatropic rearrangements, intramolecular pericyclic processes wherein one σ-bond is exchanged for another σ-bond. Example reactions are the Cope and Claisen rearrangements.

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The E2 Reaction

antiperiplanar The E2 ReactionWhen basicity and/or steric effects outweigh nucleophilicity, and a good leaving group (LG) is present, we observe elimination chemistry leading to olefins (alkenes) instead of substitution. The E2 reaction (elimination bimolecular) takes place via a concerted mechanism, and involves an antiperiplanar alignment of orbitals – proton and LG lined up across from one another however in the same plane. Continue reading

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