Metal‐Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium‐Catalyzed Hydrosilylation/Cyclization of 1,n‐Dienes by Chain Walking

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. Walk along! Sequential formation of distant bonds within a catalytic cycle was achieved for palladium‐catalyzed hydrosilylation/cyclization of various 1,n‐dienes by a nondissociative chain‐walking pathway. 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.