Copper-catalyzed highly enantioselective 1,4-conjugate addition of trimethylaluminum to 2-cyclohexenone

Abstract New bidentate phosphites were prepared starting from BINOL and H 8 -BINOL. Utilization of these ligands in the copper-catalyzed enantioselective conjugate addition of trimethylaluminum to 2-cyclohexenone afforded 3-methylcyclohexanone with up to 96% e.e. The scope of this process using various copper sources was investigated.

[1]  P. Perlmutter Conjugate Addition Reactions in Organic Synthesis , 1992 .

[2]  B. Feringa,et al.  Phosphoramidites: marvellous ligands in catalytic asymmetric conjugate addition. , 2000, Accounts of chemical research.

[3]  D. Seebach,et al.  TADDOLs, Their Derivatives, and TADDOL Analogues: Versatile Chiral Auxiliaries. , 2001, Angewandte Chemie.

[4]  B. Feringa,et al.  Highly Enantioselective Catalytic Conjugate Addition and Tandem Conjugate Addition–Aldol Reactions of Organozinc Reagents , 1997 .

[5]  A. Pfaltz,et al.  PhosphinooxazolinesA New Class of Versatile, Modular P,N-Ligands for Asymmetric Catalysis , 2000 .

[6]  H. Mizutani,et al.  Modular peptide-based phosphine ligands in asymmetric catalysis: efficient and enantioselective Cu-catalyzed conjugate additions to five-, six-, and seven-membered cyclic enones. , 2001, Journal of the American Chemical Society.

[7]  C. Claver,et al.  Copper-catalysed asymmetric 1,4-addition of organometallic reagents to 2-cyclohexenone using novel phosphine-phosphite ligands , 2000 .

[8]  I. Escher,et al.  New Chiral Oxazoline-Phosphite Ligands for the Enantioselective Copper-Catalyzed 1,4-Addition of Organozinc Reagents to Enones , 2000 .

[9]  A. Alexakis,et al.  Asymmetric conjugate addition of diethyl zinc to enones with chiral phosphorus ligands derived from TADDOL , 1998 .

[10]  A. Chan,et al.  ENANTIOSELECTIVE CONJUGATE ADDITION OF DIETHYLZINC TO CYCLIC ENONES WITH CHIRAL ARYL DIPHOSPHITE-COPPER CATALYSTS , 1999 .

[11]  Eric N. Jacobsen,et al.  Comprehensive asymmetric catalysis , 1999 .

[12]  S. Buchwald,et al.  Synthesis of β-Alkyl Cyclopentanones in High Enantiomeric Excess via Copper-Catalyzed Asymmetric Conjugate Reduction , 2000 .

[13]  B. Feringa,et al.  Carbon-Carbon Bond Formation by Catalytic Enantioselective Conjugate Addition , 1995 .

[14]  B. Feringa,et al.  Catalytic enantioselective annulations via 1,4-addition-aldol cyclization of functionalized organozinc reagents , 1999 .