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Nickel-catalyzed enantioselective vinylation of aryl 2-azaallyl anions.

ABSTRACT: A unique enantioselective nickel-catalyzed vinylation of 2-azaallyl anions is advanced for the first time. This method affords diverse vinyl aryl methyl amines with high enantioselectivities, which are frequently occurring scaffolds in natural products and medications. This C-H functionalization method can also be extended to the synthesis of enantioenriched 1,3-diamine derivatives by employing suitably elaborated vinyl bromides. Key to the success of this process is the identification of a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, all of which favor an anionic vinylation route over a background radical reaction. A telescoped gram scale synthesis and a product derivatization study confirmed the scalability and synthetic potential of this method.

SUBMITTER: Duan S

PROVIDER: S-EPMC8115067 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Nickel-catalyzed enantioselective vinylation of aryl 2-azaallyl anions.

Duan Shengzu S Deng Guogang G Zi Yujin Y Wu Xiaomei X Tian Xun X Liu Zhengfen Z Li Minyan M Zhang Hongbin H Yang Xiaodong X Walsh Patrick J PJ

Chemical science 20210326 18

A unique enantioselective nickel-catalyzed vinylation of 2-azaallyl anions is advanced for the first time. This method affords diverse vinyl aryl methyl amines with high enantioselectivities, which are frequently occurring scaffolds in natural products and medications. This C-H functionalization method can also be extended to the synthesis of enantioenriched 1,3-diamine derivatives by employing suitably elaborated vinyl bromides. Key to the success of this process is the identification of a Ni/c ...[more]

PMID: 34084440

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