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Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements.

ABSTRACT: The design, synthesis, and evaluation of bifunctional linchpins, conformationally anchored on six-membered rings to achieve efficient [1,5]-Brook rearrangements involving vinyl silanes have been achieved. The restrained linchpins were subsequently exploited in type II anion relay chemistry (ARC) to permit both alkylations and Pd-mediated cross-coupling reactions (CCR) of sp2 stabilized carbanions. DFT calculations were then employed to understand the mechanism and reactivity trends of [1,4]- and [1,5]-vinyl Brook rearrangements to provide insight on the role of the required copper reagent and the substrate geometry.

SUBMITTER: Liu Q

PROVIDER: S-EPMC5558205 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements.

Liu Qi Q Chen Yu Y Zhang Xiao X Houk K N KN Liang Yong Y Smith Amos B AB

Journal of the American Chemical Society 20170614 25

The design, synthesis, and evaluation of bifunctional linchpins, conformationally anchored on six-membered rings to achieve efficient [1,5]-Brook rearrangements involving vinyl silanes have been achieved. The restrained linchpins were subsequently exploited in type II anion relay chemistry (ARC) to permit both alkylations and Pd-mediated cross-coupling reactions (CCR) of sp<sup>2</sup> stabilized carbanions. DFT calculations were then employed to understand the mechanism and reactivity trends of ...[more]

PMID: 28613847

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