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. Synthese im Spaziergang: Die sequentielle Bildung weit entfernter Bindungen innerhalb eines Katalysekreislaufs gelingt durch Pd‐katalysierte Hydrosilylierung/Cyclierung von 1,n‐Dienen über einen nicht‐dissoziativen „Chain‐Walking“‐Mechanismus. Die Reaktion ist auf verschiedene 1,n‐Diene anwendbar, einschließlich eines 1,13‐Diens, und liefert einen Cyclopentanring sowie eine Kohlenstoff‐Silicium‐Bindung an einer entfernten Position.