Rhodium-Catalyzed Highly Regio- and Enantioselective Reductive Cyclization of Alkyne-Tethered Cyclohexadienones
journal contributionposted on 08.01.2018, 00:00 by Krishna Kumar Gollapelli, Sangeetha Donikela, Nemali Manjula, Rambabu Chegondi
Rhodium-catalyzed asymmetric hydrogenation of alkyne-tethered cyclohexadienones enables highly regio- and enantioselective reductive cyclization to afford cis-hydrobenzofurans and cis-hydroindoles in high yields. Desymmetrization of 1,3-diyne-tethered cyclohexadienones was also explored, wherein the intramolecular coordination of a Rh complex with the cyclohexadienone ring induces exclusive regioselectivity. Mechanistic studies including hydrogen–deuterium crossover experiments suggested that hydrogen activation is the rate-determining step for tandem reductive cyclization. Moreover, this highly practical and atom-economical transformation has tolerance to many functional groups with a broad range of substrate scope, allowing further transformations to expand the structural complexity of the bicyclic scaffolds.
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bicyclic scaffoldshydrogen activationcialkyne-tethered cyclohexadienonesEnantioselective Reductive CyclizationMechanistic studiessubstrate scopeenantioselective reductive cyclizationatom-economical transformationAlkyne-Tethered Cyclohexadienones Rhodium-catalyzedintramolecular coordinationtandem reductive cyclizationrate-determining stepcyclohexadienone ring