Regio- and Diastereoselective Formal [2+2] Cycloaddition of Allenes with Amino-Functionalized Alkenes by Rare-Earth-Catalyzed C(sp2)−H Activation
Wenxuan Xu
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Search for more papers by this authorCorresponding Author
Dr. Xuefeng Cong
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Kun An
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Shao-Jie Lou
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorZhenghua Li
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Masayoshi Nishiura
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorProf. Dr. Tetsuro Murahashi
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Zhaomin Hou
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorWenxuan Xu
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Search for more papers by this authorCorresponding Author
Dr. Xuefeng Cong
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Kun An
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Shao-Jie Lou
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorZhenghua Li
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorDr. Masayoshi Nishiura
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorProf. Dr. Tetsuro Murahashi
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Zhaomin Hou
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152–8552 Japan
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351–0198 Japan
Search for more papers by this authorGraphical Abstract
Half-sandwich rare-earth catalysts serve as a unique platform for the regio- and diastereoselective formal [2+2] cycloaddition of a wide range of allenes with amino-functionalized alkenes via allene C(sp2)−H activation, affording a new family of cyclobutane and cyclobutene derivatives which were difficult to access previously.
Abstract
The [2+2] cycloaddition of allenes with alkenes is of much interest and importance as a straightforward route for the construction of four-membered carbocycles but has remained much underexplored to date. Herein we report for the first time the intermolecular regio- and diastereoselective formal [2+2] cycloaddition of a wide range of allenes with amino-functionalized alkenes by half-sandwich rare-earth catalysts. The reaction proceeded through an allene C(sp2)−H activation mechanism initiated by the site-selective deprotonation of the allene unit by a rare-earth metal alkyl species followed by alkene insertion into the resulting metal-allenyl bond and the subsequent intramolecular cycloaddition to an allene C=C bond. This protocol offers a unique route for the synthesis of a new family of cyclobutane and cyclobutene derivatives which were difficult to access previously.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
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