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PCET-Enabled Olefin Hydroamidation Reactions with N-Alkyl Amides.

ABSTRACT: Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in N-alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. The feasibility of this PCET protocol in enabling the intermolecular anti-Markovnikov hydroamidation reactions of unactivated olefins is also demonstrated.

SUBMITTER: Nguyen ST

PROVIDER: S-EPMC7156045 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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PCET-Enabled Olefin Hydroamidation Reactions with <i>N</i>-Alkyl Amides.

Nguyen Suong T ST Zhu Qilei Q Knowles Robert R RR

ACS catalysis 20190417 5

Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in <i>N</i>-alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and am ...[more]

PMID: 32292642

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