biostudies-literaturePatel HHNational Institute of General Medical SciencesNIGMS NIH HHS3462-5https://www.ebi.ac.uk/biostudies/studies/S-EPMC4785804biostudies-literatureUnknown137(10)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.Journal of the American Chemical SocietyPalladium-catalyzed enantioselective Heck alkenylation of acyclic alkenols using a redox-relay strategy.PMC4785804R01GM063540R01 GM063540Patel HHSigman MSfalsePalladium-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.2015-01-01T00:00:00Z2015 Mar2025-04-26T02:17:27.911Z2019-03-27T02:10:49ZS-EPMC47858042573854810.1021/ja5130836