Aldehydes as O-Nucleophiles in Cobalt Hydride Hydrogen Atom Transfer Catalysis: Overriding the Innate Somophilicity.

In metal hydride-catalyzed alkene hydrofunctionalization reactions via hydrogen atom transfer, simple carbonyl groups have been well-recognized as good somophiles at the carbon for C-C bond formation. Here we report an alternative pathway exploring the carbonyl as an O-nucleophile to make new C-O bonds during the CoH-catalyzed oxidative cyclization of alkenyl aldehydes. This reaction provides a rapid, mild, modular, and stereoselective (up to >20:1) entry to saturated O-heterocycles via nucleophilic trapping of an in situ-formed oxocarbenium intermediate. The key to overriding the carbonyl's innate somophilicity was found to be promoting the formation of organocobalt species and suppressing the radical exchange.