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.
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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)