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Organic Chemistry

Summary

Organic ChemistrySummary

Summary

30 • Summary

30 • Summary

A pericyclic reaction takes place in a single step through a cyclic transition state without intermediates. There are three major classes of pericyclic processes: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. The stereochemistry of these reactions is controlled by the symmetry of the orbitals involved in bond reorganization.

Electrocyclic reactions involve the cyclization of conjugated acyclic polyenes. For example, 1,3,5-hexatriene cyclizes to 1,3-cyclohexadiene on heating. Electrocyclic reactions can occur by either conrotatory or disrotatory pathways, depending on the symmetry of the terminal lobes of the π system. Conrotatory cyclization requires that both lobes rotate in the same direction, whereas disrotatory cyclization requires that the lobes rotate in opposite directions. The reaction course in a specific case can be found by looking at the symmetry of the highest occupied molecular orbital (HOMO).

Cycloaddition reactions are those in which two unsaturated molecules add together to yield a cyclic product. For example, Diels–Alder reaction between a diene (four π electrons) and a dienophile (two π electrons) yields a cyclohexene. Cycloadditions can take place either by suprafacial or antarafacial pathways. Suprafacial cycloaddition involves interaction between lobes on the same face of one component and on the same face of the second component. Antarafacial cycloaddition involves interaction between lobes on the same face of one component and on opposite faces of the other component. The reaction course in a specific case can be found by looking at the symmetry of the HOMO of one component and the lowest unoccupied molecular orbital (LUMO) of the other.

Sigmatropic rearrangements involve the migration of a σ-bonded group across a π electron system. For example, Claisen rearrangement of an allylic vinylic ether yields an unsaturated carbonyl compound, and Cope rearrangement of a 1,5-hexadiene yields an isomeric 1,5-hexadiene. Sigmatropic rearrangements can occur with either suprafacial or antarafacial stereochemistry; the selection rules for a given case are the same as those for cycloaddition reactions.

The stereochemistry of any pericyclic reaction can be predicted by counting the total number of electron pairs (bonds) involved in bond reorganization and then applying the mnemonic “The Electrons Circle Around.” That is, thermal (ground-state) reactions involving an even number of electron pairs occur with either conrotatory or antarafacial stereochemistry. Exactly the opposite rules apply to photochemical (excited-state) reactions.

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