A practical method for the synthesis of highly enantioenriched trans-1,2-amino alcohols.

A highly enantioselective addition of phenyl carbamate to meso-epoxides has been developed to efficiently generate protected trans-1,2-amino alcohols. This transformation is promoted by an oligomeric (salen)Co-OTf catalyst and has been used to prepare two useful 2-aminocycloalkanol hydrochlorides in enantiopure form on a multigram scale from commercially available starting materials.

[1]  M. North,et al.  Bimetallic Aluminum(salen) Catalyzed Synthesis of Oxazolidinones from Epoxides and Isocyanates , 2013 .

[2]  E. Jacobsen,et al.  Enantioselective total synthesis of (+)-reserpine. , 2013, Organic letters.

[3]  Ryan C. Jeske,et al.  Enantioselective epoxide polymerization using a bimetallic cobalt catalyst. , 2010, Journal of the American Chemical Society.

[4]  E. Jacobsen,et al.  An enantioselective total synthesis of (+)-peloruside A. , 2010, Angewandte Chemie.

[5]  Arjan W. Kleij,et al.  Cooperative multimetallic catalysis using metallosalens. , 2010, Chemical communications.

[6]  E. Jacobsen,et al.  Enantioselective intramolecular openings of oxetanes catalyzed by (salen)Co(III) complexes: access to enantioenriched tetrahydrofurans. , 2009, Journal of the American Chemical Society.

[7]  Christopher W. Jones,et al.  Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design. , 2008, Accounts of chemical research.

[8]  Y. Yamashita,et al.  Enantioselective desymmetrization of meso epoxides with anilines catalyzed by a niobium complex of a chiral multidentate binol derivative. , 2007, Angewandte Chemie.

[9]  Christopher W. Jones,et al.  Ring-expanding olefin metathesis: a route to highly active unsymmetrical macrocyclic oligomeric co-salen catalysts for the hydrolytic kinetic resolution of epoxides. , 2007, Journal of the American Chemical Society.

[10]  D. Kahne,et al.  Degradation and reconstruction of moenomycin A and derivatives: dissecting the function of the isoprenoid chain. , 2006, Journal of the American Chemical Society.

[11]  E. Juaristi,et al.  Chiral 1,2-Amino Alcohols and 1,2-Diamines Derived from Cyclohexene Oxide: Recent Applications in Asymmetric Synthesis , 2006 .

[12]  B. Snider,et al.  Synthesis of (+)-sch 642305 by a biomimetic transannular Michael reaction. , 2006, Organic letters.

[13]  L. Zani,et al.  Resolution of racemic 2-aminocyclohexanol derivatives and their application as ligands in asymmetric catalysis. , 2006, The Journal of organic chemistry.

[14]  Armando Carlone,et al.  Direct catalytic synthesis of enantiopure 5-substituted oxazolidinones from racemic terminal epoxides. , 2005, Organic letters.

[15]  J. Collin,et al.  Enantioselective ring opening of meso-epoxides by aromatic amines catalyzed by lanthanide iodo binaphtholates. , 2005, Organic letters.

[16]  C. Schneider,et al.  Scandium-bipyridine-catalyzed enantioselective addition of alcohols and amines to meso-epoxides. , 2004, Angewandte Chemie.

[17]  Armando Carlone,et al.  Asymmetric catalytic synthesis of enantiopure N-protected 1,2-amino alcohols. , 2004, Organic letters.

[18]  S. Buchwald,et al.  Palladium-catalyzed regioselective hydrodebromination of dibromoindoles: application to the enantioselective synthesis of indolodioxane U86192A. , 2004, The Journal of organic chemistry.

[19]  D. Blackmond,et al.  Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides. , 2004, Journal of the American Chemical Society.

[20]  E. Jacobsen,et al.  New oligomeric catalyst for the hydrolytic kinetic resolution of terminal epoxides under solvent-free conditions , 2003 .

[21]  E. Jacobsen,et al.  A practical oligomeric [(salen)Co] catalyst for asymmetric epoxide ring-opening reactions. , 2002, Angewandte Chemie.

[22]  E. Jacobsen,et al.  Highly active oligomeric (salen)co catalysts for asymmetric epoxide ring-opening reactions. , 2001, Journal of the American Chemical Society.

[23]  R. Breinbauer,et al.  Cooperative Asymmetric Catalysis with Dendrimeric [Co(salen)] Complexes , 2000 .

[24]  M. Lemaire,et al.  Nitrogen-containing ligands for asymmetric homogeneous and heterogeneous catalysis. , 2000, Chemical reviews.

[25]  S. Bergmeier The Synthesis of Vicinal Amino Alcohols , 2000 .

[26]  Eric N. Jacobsen,et al.  Polymer-Supported Chiral Co(Salen) Complexes: Synthetic Applications and Mechanistic Investigations in the Hydrolytic Kinetic Resolution of Terminal Epoxides , 1999 .

[27]  S. Schaus,et al.  Practical Synthesis of Enantiopure Cyclic 1,2-Amino Alcohols via Catalytic Asymmetric Ring Opening of Meso Epoxides , 1997 .

[28]  E. Jacobsen,et al.  On the Mechanism of Asymmetric Nucleophilic Ring-Opening of Epoxides Catalyzed by (Salen)CrIII Complexes , 1996 .

[29]  D. Ager,et al.  1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis. , 1996, Chemical reviews.

[30]  L. Martínez,et al.  Highly Enantioselective Ring Opening of Epoxides Catalyzed by (salen)Cr(III) Complexes , 1995 .

[31]  W. A. Nugent Chiral Lewis acid catalysis. Enantioselective addition of azide to meso epoxides , 1992 .

[32]  L. Overman,et al.  A convenient method for obtaining trans-2-aminocyclohexanol and trans-2-aminocyclopentanol in enantiomerically pure form , 1985 .

[33]  Norman L. Allinger,et al.  Conformational analysis. LXIX. Improved force field for the calculation of the structures and energies of hydrocarbons , 1971 .

[34]  Richard H. Boyd,et al.  Heats of combustion and strain energies of bicyclo[n.m.O]alkanes , 1970 .

[35]  S. Denmark,et al.  Synthesis and resolution of racemic trans-2-(N-benzyl)amino-1-cyclohexanol: Enantiomer separation by sequential use of (R)- and (S)-Mandelic acid: [cyclohexanol, 2-(N-benzyl)amino, (1S,2S)- and (1R,2R)-] , 2008 .