Highly Enantioselective Syntheses of Chiral β‐Amino Alcohols in the Presence of Chiral TiIV Schiff Base Complexes as Catalysts

Two new chiral Schiff bases 1 and 2 were prepared by condensation of 3,3′-di-tert-butyl-5,5′-methylenebis(salicylaldehyde) and 3,3′-dimethyl-5,5′-methylenebis(salicylaldehyde) with (1R,2S)-(–)-2-aminodiphenylethanol and were characterized by elemental analysis, 1H NMR, 13C NMR, IR, UV/Vis, and CD spectroscopy, optical rotation, and mass spectrometry. Highly enantioselective ring opening reactions of meso-stilbene oxide, cyclohexene oxide, cyclooctene oxide, and cis-butene oxide with anilines in the presence of several additives were carried out in the presence of TiIV complexes generated in situ through the interaction of Ti(OiPr)4 with chiral Schiff bases 1 and 2 at 0 °C. Excellent yields (>99 %) of chiral β-amino alcohols with high enantioselectivity (ee, >99 %) were achieved in 10 h when chiral imines were used as additives. The catalyst 1-Ti(OiPr)4 worked better than the catalyst 2-Ti(OiPr)4 in terms of reactivity and enantioselecitivity for the epoxide ring opening reactions to produce chiral β-amino alcohols in high optical purity. The chiral catalyst used in this study was recoverable and recyclable several times with retention of its performance. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

[1]  Y. Yamashita,et al.  The development of scalemic multidentate niobium complexes as catalysts for the highly stereoselective ring opening of meso-epoxides and meso-aziridines. , 2007, Journal of the American Chemical Society.

[2]  C. Schneider,et al.  Scandium–Bipyridine‐Catalyzed Enantioselective Aminolysis of meso‐Epoxides , 2007 .

[3]  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.

[4]  C. Schneider.  Synthesis of 1,2-Difunctionalized Fine Chemicals Through Catalytic, Enantioselective Ring-Opening Reactions of Epoxides , 2006 .

[5]  R. I. Kureshy,et al.  Asymmetric addition of trimethylsilyl cyanide to aldehydes promoted by chiral polymeric vanadium(V) salen complex as an efficient and recyclable catalyst , 2006 .

[6]  R. I. Kureshy,et al.  Enantioselective aminolytic kinetic resolution (AKR) of epoxides catalyzed by recyclable polymeric Cr(III) salen complexes , 2006 .

[7]  R. I. Kureshy,et al.  Facile Enantioselective Ring‐Opening Reaction of meso Epoxides with Anilines Using (S)‐(–)‐BINOL‐Ti Complex as a Catalyst , 2006 .

[8]  R. Shukla,et al.  A novel effective hydration of carbon monoxide in liquid phase by a water-soluble ruthenium complex catalyst at moderate pressures in aqueous medium , 2005 .

[9]  K. Manabe,et al.  Catalytic asymmetric ring opening of meso-epoxides with aromatic amines in water. , 2005, Organic letters.

[10]  Isidro M. Pastor,et al.  Asymmetric Ring Opening of Epoxides , 2005 .

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

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

[13]  J. Collin,et al.  Samarium iodides catalyzed meso-epoxides ring opening by aromatic amines , 2004 .

[14]  Armando Carlone,et al.  Asymmetric aminolysis of aromatic epoxides: a facile catalytic enantioselective synthesis of anti-beta-amino alcohols. , 2004, Organic letters.

[15]  Shuichi Nakamura,et al.  A new approach to enantioselective cyanation of imines with Et2AlCN , 2004 .

[16]  T. Pilati,et al.  Stereoselective synthesis of heterosubstituted aziridines and their functionalization , 2004 .

[17]  R. I. Kureshy,et al.  Dicationic chiral Mn(III) salen complex exchanged in the interlayers of montmorillonite clay: a heterogeneous enantioselective catalyst for epoxidation of nonfunctionalized alkenes , 2004 .

[18]  M. Bandini,et al.  Kinetic resolution of epoxides by a C-C bond-forming reaction: highly enantioselective addition of indoles to cis, trans, and meso aromatic epoxides catalyzed by [Cr(salen)] complexes. , 2004, Angewandte Chemie.

[19]  R. Shukla,et al.  Chiral Mn(III) salen complex-catalyzed enantioselective epoxidation of nonfunctionalized alkenes using urea–H2O2 adduct as oxidant , 2003 .

[20]  B. Trost,et al.  A direct catalytic asymmetric mannich-type reaction to syn-amino alcohols. , 2003, Journal of the American Chemical Society.

[21]  C. Barbas,et al.  A highly enantioselective amino acid-catalyzed route to functionalized α-amino acids , 2002 .

[22]  M. Shibasaki,et al.  An enantioselective formal synthesis of 4-demethoxydaunomycin using the catalytic asymmetric ring opening reaction of meso-epoxide with p-anisidine , 2002 .

[23]  E. Jacobsen,et al.  Practical Considerations in Kinetic Resolution Reactions , 2001 .

[24]  B. List.  The direct catalytic asymmetric three-component Mannich reaction , 2000 .

[25]  E. Jacobsen,et al.  CHROMIUM CATALYZED KINETIC RESOLUTION OF 2,2-DISUBSTITUTED EPOXIDES , 1999 .

[26]  P. O’Brien.  Sharpless Asymmetric Aminohydroxylation: Scope, Limitations, and Use in Synthesis. , 1999, Angewandte Chemie.

[27]  C. Senanayake,et al.  Rigid aminoalcohol backbone as a highly defined chiral template for the preparation of optically active tertiary α-hydroxyl acids , 1999 .

[28]  X. Hou,et al.  Desymmetric ring-opening of meso-epoxides with anilines: a simple way to chiral β-amino alcohols , 1998 .

[29]  Shi-hui Wu,et al.  A Regio-and Stereoselective Synthesis of β-Amino Alcohols , 1997 .

[30]  E. Corey,et al.  A Novel Chiral Super-Lewis Acidic Catalyst for Enantioselective Synthesis , 1996 .

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

[32]  Guigen Li,et al.  Catalytic Asymmetric Aminohydroxylation (AA) of Olefins , 1996 .

[33]  S. Knapp.  Synthesis of Complex Nucleoside Antibiotics , 1995 .

[34]  E. Jacobsen,et al.  A Practical Method for the Large-Scale Preparation of [N,N'-Bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediaminato(2-)]manganese(III) chloride, a Highly Enantioselective Epoxidation Catalyst , 1994 .

[35]  H. Natsugari,et al.  Stereoselective synthesis of sperabillins and related compounds , 1991 .

[36]  E. Eliel,et al.  Highly stereoselective syntheses involving N-alkyl-4,4,7.alpha.-trimethyl-trans-octahydro-1,3-benzoxazine intermediates. 2. , 1990 .

[37]  K. Matsui,et al.  Synthesis and alpha-D-glucosidase inhibitory activity of N-substituted valiolamine derivatives as potential oral antidiabetic agents. , 1986, Journal of medicinal chemistry.

[38]  M. Ohno,et al.  Stereocontrolled synthesis of (+)-negamycin from an acyclic homoallylamine by 1,3-asymmetric induction , 1982 .

[39]  R. Howe,et al.  Beta-adrenergic blocking agents. 3. The optical isomers of pronethalol, propranolol, and several related compounds. , 1968, Journal of medicinal chemistry.

[40]  J. S. Stephenson,et al.  Beta-adrenergic blocking agents. I. Pronethalol and related N-alkyl and N-aralkyl derivatives of 2-amino-1-(2-naphythyl)ethanol. , 1968, Journal of medicinal chemistry.

[41]  A F Crowther,et al.  Beta-adrenergic blocking agents. II. Propranolol and related 3-amino-1-naphthoxy-2-propanols. , 1968, Journal of medicinal chemistry.

[42]  D. D. Perrin,et al.  Purification of laboratory chemicals , 1966 .