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.