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Unusual hydroxyl effect on fulvene endoperoxide decompositions.

ABSTRACT: The thermal decomposition of fulvene endoperoxides ordinarily proceeds via an allene oxide intermediate affording oxepin-2(3H)-one derivatives. We have now uncovered new, unusual pathways in these decompositions where the presence of a hydroxyl group on the alkyl or aryl attached to the fulvene exocyclic double bond has a profound effect on the fate of the reactive intermediates derived from the unstable endoperoxides. Computational work supports the proposed mechanistic pathways.

SUBMITTER: Erden I

PROVIDER: S-EPMC4860729 | biostudies-literature | 2016 May

REPOSITORIES: biostudies-literature

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Unusual hydroxyl effect on fulvene endoperoxide decompositions.

Erden Ihsan I Basada John J Poli Daniela D Cabrera Gabriel G Xu Fupei F Gronert Scott S

Tetrahedron letters 20160501 20

The thermal decomposition of fulvene endoperoxides ordinarily proceeds via an allene oxide intermediate affording oxepin-2(<i>3H</i>)-one derivatives. We have now uncovered new, unusual pathways in these decompositions where the presence of a hydroxyl group on the alkyl or aryl attached to the fulvene exocyclic double bond has a profound effect on the fate of the reactive intermediates derived from the unstable endoperoxides. Computational work supports the proposed mechanistic pathways. ...[more]

PMID: 27175039

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