Kochi Takuya, Ichinose Kazuya, Shigekane Masayuki, Hamasaki Taro, Kakiuchi Fumitoshi
Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223-8522, Japan.
Angew Chem Int Ed Engl. 2019 Apr 8;58(16):5261-5265. doi: 10.1002/anie.201814558. Epub 2019 Mar 12.
Sequential formation of distant bonds in organic molecules was achieved for the palladium-catalyzed hydrosilylation/cyclization of various 1,n-dienes by chain walking of the metal catalyst. The reaction was applicable to various 1,n-dienes, including a 1,13-diene, to form a cyclopentane ring as well as a carbon-silicon bond at a remote site. The use of "nondissociative" chain walking provides a fascinating strategy in organic synthesis to functionalize distant parts of organic molecules, in a particular order, within a catalytic cycle by effectively moving the reactive center from a remote position.
通过金属催化剂的链行走，实现了钯催化的各种1,n -二烯的硅氢化/环化反应中有机分子中远距离键的顺序形成。该反应适用于各种1,n -二烯，包括1,13 -二烯，可形成环戊烷环以及在远程位置形成碳 - 硅键。“非解离性”链行走的应用为有机合成提供了一种引人入胜的策略，通过在催化循环内有效地将反应中心从远程位置移动，以特定顺序对有机分子的远距离部分进行官能化。
