A reductive-coupling plus Nazarov cyclization sequence in the asymmetric synthesis of five-membered carbocycles.
Palladium-mediated hydrostannylation of alkynoyl compounds is combined with Stille-Scott cross-coupling (reductive-coupling) to give one-pot access to divinyl and aryl vinyl ketones, which undergo Nazarov cyclization to give cyclopentenones upon treatment with acid. This reaction sequence has been studied with a variety of different substitution patterns, including the use of oxazolidinone auxiliaries to achieve torquoselectivity in the Nazarov cyclization. Through a combination of good yields and moderate to good levels of stereochemical induction, this approach affords efficient, convergent, and asymmetric access to a variety of different cyclopentanoid systems.
Kerr
Daniel J
DJ
Medicinal Chemistry and Drug Action, Monash Institute of Pharmaceutical Sciences, Monash University, 381 Royal Parade, Parkville Vic 3052, Australia.
White
Jonathan M
JM
Flynn
Bernard L
BL
D000480:Alkynes / Q000737:chemistry; D003500:Cyclization; D004952:Esters; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000480:Alkynes; D004952:Esters; D006844:Hydrocarbons, Cyclic; D007659:Ketones