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A divergent mechanistic course of Pd(0)-catalyzed aza-Claisen rearrangement and aza-Rautenstrauch-type cyclization of N-allyl ynamides.

ABSTRACT: A fascinating mechanistic study of ynamido-palladium-pi-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimine formation via a palladium-catalyzed aza-Rautenstrauch-type cyclization pathway.

SUBMITTER: Dekorver KA

PROVIDER: S-EPMC2862050 | biostudies-literature | 2010 Apr

REPOSITORIES: biostudies-literature

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A divergent mechanistic course of Pd(0)-catalyzed aza-Claisen rearrangement and aza-Rautenstrauch-type cyclization of N-allyl ynamides.

Dekorver Kyle A KA Hsung Richard P RP Lohse Andrew G AG Zhang Yu Y

Organic letters 20100401 8

A fascinating mechanistic study of ynamido-palladium-pi-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimine formation via a palladium-catalyzed aza-Rautenstrauch-type cyclization pathway. ...[more]

PMID: 20337418

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