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Rearrangement reactions of 1,1-divinyl-2-phenylcyclopropanes.

ABSTRACT: 1,1-Divinyl-2-phenylcyclopropanes are entry points to a rich area of rearrangement chemistry. With N,N-diallyl amide substrates, tandem radical cyclizations can be initiated at room temperature. Warming provides products of pure thermal rearrangements with acids, ester, and amides. These isomerizations give vinylcyclopentenes resulting from divinylcyclopropane rearrangements and more deeply rearranged tricyclic spirolactams resulting from aromatic Cope rearrangements followed by ene reactions. Conversion of the carbonyl group to an alcohol or ether opens retro-ene pathways followed by either tautomerization or Claisen rearrangement.

SUBMITTER: Hay EB

PROVIDER: S-EPMC4304479 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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Rearrangement reactions of 1,1-divinyl-2-phenylcyclopropanes.

Hay E Ben EB Zhang Hanmo H Curran Dennis P DP

Journal of the American Chemical Society 20141222 1

1,1-Divinyl-2-phenylcyclopropanes are entry points to a rich area of rearrangement chemistry. With N,N-diallyl amide substrates, tandem radical cyclizations can be initiated at room temperature. Warming provides products of pure thermal rearrangements with acids, ester, and amides. These isomerizations give vinylcyclopentenes resulting from divinylcyclopropane rearrangements and more deeply rearranged tricyclic spirolactams resulting from aromatic Cope rearrangements followed by ene reactions. C ...[more]

PMID: 25530073

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