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Electroreductive Olefin-Ketone Coupling.

ABSTRACT: A user-friendly approach is presented to sidestep the venerable Grignard addition to unactivated ketones to access tertiary alcohols by reversing the polarity of the disconnection. In this work a ketone instead acts as a nucleophile when adding to simple unactivated olefins to accomplish the same overall transformation. The scope of this coupling is broad as enabled using an electrochemical approach, and the reaction is scalable, chemoselective, and requires no precaution to exclude air or water. Multiple applications demonstrate the simplifying nature of the reaction on multistep synthesis, and mechanistic studies point to an intuitive mechanism reminiscent of other chemical reductants such as SmI₂ (which cannot accomplish the same reaction).

SUBMITTER: Hu P

PROVIDER: S-EPMC8353665 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Electroreductive Olefin-Ketone Coupling.

Hu Pengfei P Peters Byron K BK Malapit Christian A CA Vantourout Julien C JC Wang Pan P Li Jinjun J Mele Lucas L Echeverria Pierre-Georges PG Minteer Shelley D SD Baran Phil S PS

Journal of the American Chemical Society 20201201 50

A user-friendly approach is presented to sidestep the venerable Grignard addition to unactivated ketones to access tertiary alcohols by reversing the polarity of the disconnection. In this work a ketone instead acts as a nucleophile when adding to simple unactivated olefins to accomplish the same overall transformation. The scope of this coupling is broad as enabled using an electrochemical approach, and the reaction is scalable, chemoselective, and requires no precaution to exclude air or water ...[more]

PMID: 33259715

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