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Enzyme-Catalyzed Asymmetric Primary Amination of Benzylic and Allylic C(sp3)–H Bonds
Enzymatic Primary Amination of Benzylic and Allylic C(sp3)–H Bonds.
J. Am. Chem. Soc. 2020;
21 July 2020 (online)
Key wordsamines - directed evolution - cytochrome P411 hydroxylamines - amination - C–H bond activation
The Arnold group reports the directed evolution of P411-B2 to give efficient benzylic (P411BPA) and allylic (P411APA) C–H aminases. By using hydroxylamine derivatives as nitrogen sources under anaerobic conditions, the authors converted a variety of benzylic and allylic C(sp3)–H bonds into primary amines in good yields with high chemo- and enantioselectivities and promising regioselectivities.
This work represents a milestone in the development of a general C–H amination reaction. Mechanistic investigations are highly desirable in further developing this method to overcome the limitation toward alkyl-substituted allyl systems. In addition, this work encourages and challenges other groups to develop small-molecule catalysts to enable this reaction.