%0 Journal Article
%A O’Brien, Jeannette M.
%A Lee, Kang-sang
%A Hoveyda, Amir H.
%D 2010
%T Enantioselective Synthesis of Boron-Substituted Quaternary Carbons by NHC−Cu-Catalyzed Boronate Conjugate Additions to Unsaturated Carboxylic Esters, Ketones, or Thioesters
%U https://acs.figshare.com/articles/journal_contribution/Enantioselective_Synthesis_of_Boron_Substituted_Quaternary_Carbons_by_NHC_Cu_Catalyzed_Boronate_Conjugate_Additions_to_Unsaturated_Carboxylic_Esters_Ketones_or_Thioesters/2743672
%R 10.1021/ja104777u.s002
%2 https://ndownloader.figshare.com/files/4421560
%K enantioselective boronate conjugate additions
%K ketone aldol products
%K thioester
%K vs carboxylic esters
%K NHC
%K carboxylic esters
%K Unsaturated Carboxylic Esters
%X A Cu-catalyzed method for enantioselective boronate conjugate additions to trisubstituted alkenes of acyclic α,β-unsaturated carboxylic esters, ketones, and thioesters is disclosed. All transformations are promoted by 5 mol % of a chiral monodentate NHC−Cu complex, derived from a readily available C1-symmetric imidazolinium salt, and in the presence of commercially available bis(pinacolato)diboron. Reactions are efficient (typically, 60% to >98% yield after purification) and deliver the desired β-boryl carbonyls in up to >98:2 enantiomer ratio (er). Processes involving unsaturated thioesters proceed with higher enantioselectivity (vs carboxylic esters or ketones), and the resulting products can be functionalized by Ag-mediated or Pd-catalyzed reactions that furnish the derived carboxylic ester or various ketones. Routine oxidation affords β-hydroxy ketones or carboxylic esters, ketone aldol products that cannot be otherwise prepared efficiently by an alternative catalytic enantioselective protocol.
%I ACS Publications