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Competitive [2,3]- and [1,2]-oxonium ylide rearrangements. Concerted or stepwise?

ABSTRACT: The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone-5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.

SUBMITTER: Jaber DM

PROVIDER: S-EPMC3321102 | biostudies-literature | 2012 Apr

REPOSITORIES: biostudies-literature

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Competitive [2,3]- and [1,2]-oxonium ylide rearrangements. Concerted or stepwise?

Jaber Deana M DM Burgin Ryan N RN Helper Matthew M Zavalij Peter Y PY Doyle Michael P MP

Organic letters 20120312 7

The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone-5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements. ...[more]

PMID: 22409577

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