Photocatalytic Sulfonylcarbocyclization of Alkynes Using SEt as a Traceless Directing Group: Access to Cyclopentenes and Indenes
Yulu Zhou
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorYizhou Qin
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorQinggui Wang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorDr. Zuxiao Zhang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Gangguo Zhu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorYulu Zhou
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorYizhou Qin
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorQinggui Wang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorDr. Zuxiao Zhang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Gangguo Zhu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua, 321004 P. R. China
Search for more papers by this authorIn memory of Professor Ei-ichi Negishi
Abstract
Cyclopentenes and indenes are important structural scaffolds in synthetic, medical, and material chemistry. Cyclization of alkynes via remote C−H functionalization is an appealing approach to construct these motifs due to its high efficiency and step-economy. Herein, a traceless directing group strategy was designed to reverse the regioselectivity of radical addition which enabled an unprecedented photocatalytic sulfonylcarbocyclization of terminal alkynes by forming C−C bond on inert C(sp3)−H bond. It offers a facile access to decorated cyclopentenes and indenes under mild conditions. The resultant products could be converted into a set of valuable molecular scaffolds, including a key intermediate of AM-6226. Mechanistic experiments suggest a radical cascade pathway comprising a Markovnikov-type sulfonylation, 1,5-hydrogen atom transfer, 5-endo-trig cyclization, and β-elimination. This study lays further groundwork for the use of anti-Baldwin 5-endo-trig radical cyclization in rapidly assembling five-membered carbocycles.
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