A tetradentate ligand for the enantioselective Ti(IV)-promoted oxidation of sulfides to sulfoxides: origin of enantioselectivity.

A detailed stereomechanistic analysis has led to the design of a new tetradentate ligand for the enantioselective Ti(IV)-catalyzed oxidation of unsymmetrical sulfides to sulfoxides with high selectivity. The pathway of this oxidation and the closely related and long-known Kagan-Modena oxidation have been clarified to identify the likely origin of the enantioselectivity.

[1]  Elżbieta Wojaczyńska,et al.  Enantioselective synthesis of sulfoxides: 2000-2009. , 2010, Chemical reviews.

[2]  Hans-Jürgen Federsel,et al.  Mechanism of the Asymmetric Sulfoxidation in the Esomeprazole Process : Effects of the Imidazole Backbone for the Enantioselection , 2009 .

[3]  Hualiang Jiang,et al.  A density-functional study of the mechanism for the diastereoselective epoxidation of chiral allylic alcohols by the titanium peroxy complexes. , 2002, The Journal of organic chemistry.

[4]  B. Fieldhouse,et al.  On the structure of the Kagan–Modena catalysts for asymmetric oxidation of sulfides , 1999 .

[5]  J. Lohrenz,et al.  [Lithium tert-butylperoxide]12 : Crystal Structure of an Aggregated Oxenoid. , 1996, Chemistry.

[6]  J. Brunel,et al.  Catalytic Asymmetric Oxidation of Sulfides With High Enantioselectivities , 1996 .

[7]  G. Boche,et al.  [((η2-tert-Butylperoxo)titanatrane)2· 3 Dichloromethane]: X-ray Crystal Structure and Oxidation Reactions , 1996 .

[8]  J. Brunel,et al.  Highly Enantioselective Oxidation of Sulfides Mediated by a Chiral Titanium Complex , 1995 .

[9]  E. Corey On the origin of enantioselectivity in the Katsuki-Sharpless epoxidation procedure , 1990 .

[10]  S Zhao,et al.  Nonlinear effects in asymmetric synthesis. Examples in asymmetric oxidations and aldolization reactions. , 1986, Journal of the American Chemical Society.

[11]  H. Kagan,et al.  A short route to chiral sulfoxides using titanium-mediated asymmetric oxidation , 1985 .

[12]  F. Furia,et al.  Synthesis of Chiral Sulfoxides by Metal-Catalyzed Oxidation with t-Butyl Hydroperoxide , 1984 .

[13]  H. Kagan,et al.  An efficient asymmetric oxidation of sulfides to sulfoxides , 1984 .

[14]  K. Sharpless,et al.  On the mechanism of titanium-tartrate catalyzed asymmetric epoxidation , 1983 .

[15]  E. Corey,et al.  The Stereochemistry of Complex Inorganic Compounds. XXII. Stereospecific Effects in Complex Ions1 , 1959 .

[16]  G. P. Moss Basic terminology of stereochemistry (IUPAC Recommendations 1996) , 1996 .

[17]  M. Finn,et al.  Mechanism of asymmetric epoxidation. 1. Kinetics , 1991 .

[18]  M. Finn,et al.  Mechanism of asymmetric epoxidation. 2. Catalyst structure , 1991 .

[19]  H. Kagan,et al.  Asymmetric oxidation of sulfides mediated by chiral titanium complexes : mechanistic and synthetic aspects , 1987 .