Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes

Xiang Lyu, Jianbo Zhang, Dongwook Kim, Sangwon Seo* and Sukbok Chang*

*Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 34141, South Korea, Email: s.seokaist.ac.kr, sbchangkaist.ac.kr

X. Lyu, J. Zhang, D. Kim, S. Seo, S. Chang, J. Am. Chem. Soc., 2021, 143, 5867-5877.

DOI: 10.1021/jacs.1c01138

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Abstract

A NiH-catalyzed strategy for the hydroamidation of alkynes with dioxazolones allows convenient access to synthetically useful secondary enamides in (E)-anti-Markovnikov or Markovnikov selectivity. The reaction is viable for both terminal and internal alkynes and also tolerates a range of functional groups. The presence of H₂O is crucial for high catalyst turnovers.

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proposed mechanism (updated version, Feb, 14th, 2022)

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Key Words

Enamines, DMMS

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ID: J48-Y2021