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Enantioselective Synthesis of Boron-Substituted Quaternary Carbons by NHC−Cu-Catalyzed Boronate Conjugate Additions to Unsaturated Carboxylic Esters, Ketones, or Thioesters

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journal contribution
posted on 11.08.2010, 00:00 authored by Jeannette M. O’Brien, Kang-sang Lee, Amir H. Hoveyda
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.