Palladium-catalyzed enantioselective Heck alkenylation of acyclic alkenols using a redox-relay strategy.
We report a highly enantioselective intermolecular Heck reaction of alkenyl triflates and acyclic primary or racemic secondary alkenols. The mild reaction conditions permit installation of a wide range of alkenyl groups at positions β, γ, or δ to a carbonyl group in high enantioselectivity. The success of this reaction is attributed to the use of electron-withdrawing alkenyl triflates, which offer selective β-hydride elimination followed by migration of the catalyst through the alkyl chain to give the alkenylated carbonyl products. The synthetic utility of the process is demonstrated by a two-step modification of a reaction product to yield a tricyclic core structure, present in various natural products.
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
Harshkumar H
HH
Patel
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
Matthew S
MS
Sigman
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D010165:Palladium