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Aldehydes as O-Nucleophiles in Cobalt Hydride Hydrogen Atom Transfer Catalysis: Overriding the Innate Somophilicity
Yi-Chen Nie1, Fan Yang1, Yu-Hao Li1
1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Abstract:
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.
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