Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.
An efficient Cu-catalyzed protocol for enantioselective addition of a dimethylphenylsilanyl group to a wide range of cyclic and acyclic unsaturated ketones, esters, acrylonitriles, and alpha,beta,gamma,delta-dienones is disclosed. Reactions are performed in the presence of 1-2 mol % of commercially available and inexpensive CuCl, a readily accessible monodentate imidazolinium salt, and commercially available (dimethylphenylsilyl)pinacolatoboron. Cu-catalyzed enantioselective conjugate additions proceed to completion within only 2 h to afford the desired silanes in 87-97% yield and 90:10-99:1 enantiomeric ratio (er). Use of a proton source (e.g., MeOH) is not required; accordingly, synthetically versatile alpha-silyl boron enolates can be obtained. The special utility of the present protocol, in comparison with the related catalytic enantioselective aldol and boronate conjugate additions, is discussed and illustrated through various functionalizations of the enantiomerically enriched beta-silylcarbonyls.
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Kang-Sang
KS
Lee
Amir H
AH
Hoveyda
D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D006571:Heterocyclic Compounds; D007659:Ketones; D009942:Organometallic Compounds; D012821:Silanes; C030011:carbene; D003300:Copper; D008697:Methane