Mn2(CO)10-catalyzed direct protic hydrogen transfer with unactivated alkenesOA
Transition-metal-catalyzed hydrogen-atom-transfer(HAT)reactions have proven to be effective strategies for obtaining important heterocycle scaffolds found in natural products.However,the electronic mismatch between metal catalysts and the protic hydrogen atom necessitates the use of excess oxidants and external reductive hydrogen sources in existing methods,which limit their practicality.To address this issue,we present a practical and efficient methodology for Mn₂(CO)₁₀-catalyzed intramolecular transfer of the protic hydrogen atom.A catalytic amount of tBuOOH is utilized promoting the HAT process,going beyond mere oxidation,thereby obviating the need for excess oxidants and external reductive hydrogen sources during the HAT process.Additionally,the dimeric manganese catalysis enables efficient dioxygenation,oxy-amination,oxy-sulfuration,and oxy-halogenation of alkenes.Comprehensive mechanistic studies have been done and suggest that a radical reaction pathway is involved in the proton transfer.This finding provides novel insights into the direct metal-catalyzed protic hydrogen atom-transfer reactions.
Tao Li;Han Sun;Ting Shao;Albert S.C.Chan;Shan-Shui Meng
Chongqing Institute of Green and Intelligent Technology,Chongqing School,University of Chinese Academy of Sciences(UCAS Chongqing),Chongqing 400714,China University of Chinese Academy of Sciences,Beijing 100049,ChinaSchool of Pharmaceutical Sciences,Sun Yat-sen University,Guangzhou 510006,ChinaSchool of Pharmaceutical Sciences,Guangzhou University of Chinese Medicine,Guangzhou 510006,ChinaSchool of Pharmaceutical Sciences,Sun Yat-sen University,Guangzhou 510006,China Chongqing Institute of Green and Intelligent Technology,Chongqing School,University of Chinese Academy of Sciences(UCAS Chongqing),Chongqing 400714,China University of Chinese Academy of Sciences,Beijing 100049,ChinaSchool of Pharmaceutical Sciences,Sun Yat-sen University,Guangzhou 510006,China
化学化工
Manganese-catalysisUnactivated alkenesHydrogen-atom transferDual functionalizationsRadical reaction
《Green Synthesis and Catalysis》 2026 (2)
P.205-210,6
Natural Science Foundation of Guangdong Province(Nos.2022A1515010597 and 2023A1515030244)GBRCE for Functional Molecular Engineering and Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery(No.2019B030301005)for financial support of this program.
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