A mechanistically guided design leads to the synthesis of an efficient and practical new reagent for the highly enantioselective, catalytic dihydroxylation of olefins.

[structure: see text] The catalytic asymmetric dihydroxylation of olefins has been accomplished with high enantioselectivities using a proline-based catalyst. The pre-transition-state assembly for styrene is shown.

[1]  E. Corey,et al.  Highly effective transition structure designed catalyst for the enantio- and position-selective dihydroxylation of polyisoprenoids. , 2001, Organic letters.

[2]  Wirth.  Oxygen and Osmium-A New Alliance for Dihydroxylations? , 2000, Angewandte Chemie.

[3]  E. Corey,et al.  A Critical Analysis of the Mechanistic Basis of Enantioselectivity in the Bis-Cinchona Alkaloid Catalyzed Dihydroxylation of Olefins , 1996 .

[4]  E. Corey,et al.  X-ray Crystal and NMR Structure of a Highly Reactive Bidentate 1,2-Diamine−OsO4 Complex, Formally a 20-Electron Outer Valence Shell Species. Mechanistic Implications for the 1,2-Diamine-Accelerated Dihydroxylation of Olefins by OsO4 , 1996 .

[5]  E. Corey,et al.  Experimental test of the [3+2]- and [2+2]-cycloaddition pathways for the bis-cinchona alkaloid-OsO4 catalyzed dihydroxylation of olefins by means of 12C13C kinetic isotope effects , 1996 .

[6]  E. Corey,et al.  IMPROVED ENANTIOSELECTIVE DIHYDROXYLATION OF BISHOMOALLYLIC ALCOHOL DERIVATIVES USING A MECHANISTICALLY INSPIRED BIS-CINCHONA ALKALOID CATALYST , 1996 .

[7]  E. Corey,et al.  Kinetic Investigations Provide Additional Evidence That an Enzyme-like Binding Pocket Is Crucial for High Enantioselectivity in the Bis-Cinchona Alkaloid Catalyzed Asymmetric Dihydroxylation of Olefins , 1996 .

[8]  E. Corey,et al.  A mechanistically designed bis-cinchona alkaloid ligand allows position- and enantioselective dihydroxylation of farnesol and other oligoprenyl derivatives at the terminal isopropylidene unit , 1995 .

[9]  E. Corey,et al.  The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives. , 1995 .

[10]  E. Corey,et al.  Kinetic Resolution by Enantioselective Dihydroxylation of Secondary Allylic 4-Methoxybenzoate Esters Using a Mechanistically Designed Cinchona Alkaloid Catalyst , 1995 .

[11]  E. Corey,et al.  HIGHLY ENANTIOSELECTIVE AND REGIOSELECTIVE CATALYTIC DIHYDROXYLATION OF HOMOALLYLIC ALCOHOL DERIVATIVES , 1995 .

[12]  M. VanNieuwenhze,et al.  Catalytic Asymmetric Dihydroxylation , 1994 .

[13]  E. Corey,et al.  A mechanistically designed mono-cinchona alkaloid is an excellent catalyst for the enantioselective dihydroxylation of olefins , 1994 .

[14]  E. Corey,et al.  X-ray crystallographic studies provide additional evidence that an enzyme-like binding pocket is crucial to the enantioselective dihydroxylation of olefins by OsO4—bis-cinchona alkaloid complexes , 1994 .

[15]  E. Corey,et al.  Rigid and highly enantioselective catalyst for the dihydroxylation of olefins using osmium tetraoxide clarifies the origin of enantiospecificity , 1993 .

[16]  E. Corey,et al.  The origin of high enantioselectivity in the dihydroxylation of olefins using osmium tetraoxide and cinchona alkaloid catalysts , 1993 .

[17]  Jens Hartung,et al.  The Osmium-Catalyzed Asymmetric Dihydroxylation: A New Ligand Class and a Process Improvement , 1992 .