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Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes.

ABSTRACT: Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including ?-allenyl ketones and amino-substituted heterocycles.

SUBMITTER: Chuprakov S

PROVIDER: S-EPMC3999524 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes.

Chuprakov Stepan S Worrell Brady T BT Selander Nicklas N Sit Rakesh K RK Fokin Valery V VV

Journal of the American Chemical Society 20131217 1

Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoi ...[more]

PMID: 24295389

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