biostudies-literatureAlexy EJCalifornia Institute of TechnologyGordon and Betty Moore FoundationNational Institute of General Medical SciencesNIGMS NIH HHSDivision of Graduate Education10109-10112https://www.ebi.ac.uk/biostudies/studies/S-EPMC6103296biostudies-literatureUnknown140(32)The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted acyclic enol carbonates providing linear α-quaternary ketones is reported. Investigation into the reaction revealed that the use of an electron-deficient phosphinooxazoline ligand renders the enolate geometry of the starting material inconsequential, with the same enantiomer of product obtained in the same level of selectivity regardless of the starting ratio of enolates. As a result, a general method toward acyclic all-carbon quaternary stereocenters has been developed.Journal of the American Chemical SocietyCatalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates.PMC6103296R01GM080269R01 GM080269Alexy EJStoltz BMZhang HfalseCatalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates.The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted acyclic enol carbonates providing linear α-quaternary ketones is reported. Investigation into the reaction revealed that the use of an electron-deficient phosphinooxazoline ligand renders the enolate geometry of the starting material inconsequential, with the same enantiomer of product obtained in the same level of selectivity regardless of the starting ratio of enolates. As a result, a general method toward acyclic all-carbon quaternary stereocenters has been developed.2018-01-01T00:00:00Z2018 Aug2025-04-04T01:34:05.745Z2019-08-20T07:00:37ZS-EPMC61032963004921310.1021/jacs.8b05560