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Enantioselective Amino- and Oxycyanation of Alkenes via Organic Photoredox and Copper Catalysis.

ABSTRACT: The β-amino nitrile moiety and its derivatives frequently appear in natural product synthesis, in drug design, and as ligands in asymmetric catalysis. Herein, we describe a direct route to these complex motifs through the amino- and oxycyanation of olefins utilizing an acridinium photooxidant in conjunction with copper catalysis. The transformation can be rendered asymmetric by using a serine-derived bisoxazoline ligand. Mechanistic studies implicate olefin-first oxidation. The scope of amines for the aminocyanation reaction has been greatly expanded by undergoing a cation radical intermediate as opposed to previous N-centered radical-initiated aminocyanations. Furthermore, alkyl carboxylic acids were included as nucleophiles in this type of transformation for the first time without any decarboxylative side reactions.

SUBMITTER: Qian S

PROVIDER: S-EPMC10962007 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Enantioselective Amino- and Oxycyanation of Alkenes via Organic Photoredox and Copper Catalysis.

Qian Siran S Lazarus Tanya M TM Nicewicz David A DA

Journal of the American Chemical Society 20230814 33

The β-amino nitrile moiety and its derivatives frequently appear in natural product synthesis, in drug design, and as ligands in asymmetric catalysis. Herein, we describe a direct route to these complex motifs through the amino- and oxycyanation of olefins utilizing an acridinium photooxidant in conjunction with copper catalysis. The transformation can be rendered asymmetric by using a serine-derived bisoxazoline ligand. Mechanistic studies implicate olefin-first oxidation. The scope of amines f ...[more]

PMID: 37579080

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