Synthesis of Novel Amino‐Acid‐Derived Sulfinamides and Their Evaluation as Ligands for the Enantioselective Transfer Hydrogenation of Ketones

Novel chiral mono-sulfinyl diamines bearing a stereogenic sulfur atom were prepared in moderate to good yields starting from amino acids by means of a reductive amination of the corresponding amino aldehydes. Their potential as ligands for asymmetric catalysis was evaluated in the metal-catalyzed enantioselective transfer hydrogenation of alkyl-aryl ketones. The catalysts were generated in situ from sulfinamides 1a–i and arene complexes of rhodium and ruthenium, and the catalytic reductions led to the formation of chiral alcohols with up to 91 % ee. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

[1]  Jian Sun,et al.  Rationally-Designed S-Chiral Bissulfinamides as Highly Enantioselective Organocatalysts for Reduction of Ketimines , 2008 .

[2]  J. Ellman,et al.  Enantioselective aza-Henry reaction with an N-sulfinyl urea organocatalyst. , 2007, Journal of the American Chemical Society.

[3]  T. Ikariya,et al.  Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts. , 2007, Accounts of chemical research.

[4]  François Debaene,et al.  Expanding the scope of PNA-encoded libraries: divergent synthesis of libraries targeting cysteine, serine and metallo-proteases as well as tyrosine phosphatases , 2007 .

[5]  M. Reves,et al.  N-phosphino sulfinamide ligands: an efficient manner to combine sulfur chirality and phosphorus coordination behavior. , 2007, Angewandte Chemie.

[6]  K. Tan,et al.  Indium-mediated asymmetric allylation of acylhydrazones using a chiral urea catalyst. , 2007, Angewandte Chemie.

[7]  Jian Sun,et al.  S-chiral sulfinamides as highly enantioselective organocatalysts. , 2006, Organic letters.

[8]  H. Adolfsson,et al.  Enantioswitchable catalysts for the asymmetric transfer hydrogenation of aryl alkyl ketones. , 2006, Organic letters.

[9]  D. Morton,et al.  Chiral non-racemic sulfinimines: versatile reagents for asymmetric synthesis , 2006 .

[10]  T. Privalov,et al.  The importance of alkali cations in the [{RuCl2(p-cymene)}2]-pseudo-dipeptide-catalyzed enantioselective transfer hydrogenation of ketones. , 2006, Chemistry.

[11]  Elisabetta Alberico,et al.  Asymmetric transfer hydrogenation: chiral ligands and applications. , 2006, Chemical Society reviews.

[12]  Bin Yang,et al.  Asymmetric Synthesis of Heterocycles Using Sulfinimines (N-Sulfinyl Imines) , 2006 .

[13]  Arun K. Ghosh,et al.  Design and synthesis of peptidomimetic severe acute respiratory syndrome chymotrypsin-like protease inhibitors. , 2005, Journal of medicinal chemistry.

[14]  H. Adolfsson,et al.  In situ formation of ligand and catalyst--application in ruthenium-catalyzed enantioselective reduction of ketones. , 2005, Chemical communications.

[15]  A. Córdova,et al.  Novel organic catalysts for the direct enantioselective α-oxidation of carbonyl compounds , 2005 .

[16]  Isidro M. Pastor,et al.  2-(aminomethyl)-oxazolines: highly modular scaffolds for the preparation of novel asymmetric ligands. , 2005, The Journal of organic chemistry.

[17]  F. A. Davis,et al.  Recent Advances in Asymmetric Reactions Using Sulfinimines (N-Sulfinyl Imines) , 2004 .

[18]  H. Adolfsson,et al.  N-Arenesulfonyl-2-aminomethylpyrrolidines Novel Modular Ligands and Organocatalysts for Asymmetric Catalysis , 2004 .

[19]  Kentaro Kawai,et al.  N-Phosphano nitrogen-containing five-membered aromatic chiral α-sulfoxides as new chiral ligands in asymmetric palladium-catalyzed allylic alkylation: stereoelectronic effects of the substituents on the aromatic rings , 2004 .

[20]  J. Ellman,et al.  Application of P,N-sulfinyl imine ligands to iridium-catalyzed asymmetric hydrogenation of olefins. , 2004, The Journal of organic chemistry.

[21]  Isidro M. Pastor,et al.  Highly enantioselective ruthenium-catalyzed reduction of ketones employing readily available Peptide ligands. , 2004, Chemistry.

[22]  C. Solans,et al.  Stereoselective aldol additions catalyzed by dihydroxyacetone phosphate-dependent aldolases in emulsion systems: preparation and structural characterization of linear and cyclic iminopolyols from aminoaldehydes. , 2003, Chemistry.

[23]  Isidro M. Pastor,et al.  Employing the structural diversity of nature: development of modular dipeptide-analogue ligands for ruthenium-catalyzed enantioselective transfer hydrogenation of ketones. , 2003, Chemistry.

[24]  N. Khiar,et al.  Recent developments in the synthesis and utilization of chiral sulfoxides. , 2003, Chemical reviews.

[25]  J. Ellman,et al.  Novel sulfinyl imine ligands for asymmetric catalysis. , 2003, Organic letters.

[26]  A. Souers,et al.  The preparation and utility of bis(sulfinyl)imidoamidine ligands for the copper-catalyzed Diels-Alder reaction. , 2003, Journal of Organic Chemistry.

[27]  J. Ellman,et al.  Applications of tert-butanesulfinamide in the asymmetric synthesis of amines , 2003 .

[28]  Isidro M. Pastor,et al.  Novel simple and highly modular ligands for efficient asymmetric transfer-hydrogenation of ketones. , 2002, Chemical communications.

[29]  J. Ellman,et al.  N-tert-butanesulfinyl imines: versatile intermediates for the asymmetric synthesis of amines. , 2002, Accounts of chemical research.

[30]  N. Finney,et al.  A simple and advantageous protocol for the oxidation of alcohols with O-iodoxybenzoic acid (IBX). , 2002, Organic letters.

[31]  G. Prakash,et al.  Stereoselective synthesis of trifluoromethylated vicinal ethylenediamines with alpha-amino N-tert-butanesulfinimines and TMSCF3. , 2002, Journal of the American Chemical Society.

[32]  Isidro M. Pastor,et al.  Novel highly modular C2-symmetric oxazoline ligands—application in titanium-catalyzed diethylzinc additions to aldehydes , 2002 .

[33]  O. G. Mancheño,et al.  2-amino-substituted 1-sulfinylferrocenes as chiral ligands in the addition of diethylzinc to aromatic aldehydes. , 2002, The Journal of organic chemistry.

[34]  Kazuhiro Watanabe,et al.  New chiral sulfoxide ligands in catalytic asymmetric Diels–Alder reactions: double acceleration by the chiralities of the sulfoxides and oxazolines , 2001 .

[35]  A. Oliver,et al.  Synthesis, Utility, and Structure of Novel Bis(sulfinyl)imidoamidine Ligands for Asymmetric Lewis Acid Catalysis , 2001 .

[36]  G. Bárány,et al.  Solid-phase synthesis of C-terminal peptide aldehydes from amino acetals anchored to a backbone amide linker (BAL) handle , 2000 .

[37]  Yoshio Suzuki,et al.  New Chiral Sulfoxide Ligands Possessing a Phosphano or Phosphanoamino Functionality in Palladium-Catalyzed Asymmetric Allylic Nucleophilic Substitution Reactions , 2000 .

[38]  Petra,et al.  Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation , 2000, The Journal of organic chemistry.

[39]  K. Shoemaker,et al.  Solid phase synthesis of peptide aldehyde protease inhibitors. Probing the proteolytic sites of hepatitis C virus polyprotein , 2000 .

[40]  S. Steurer,et al.  Aminoalkyl‐Substituted α‐Methylene‐γ‐butyrolactones from α‐Amino Acids Using an Indium‐Mediated Barbier Allyl Addition , 1999 .

[41]  D. Iyengar,et al.  A novel, simple, chemoselective and practical protocol for the reduction of azides using In/NH4Cl , 1999 .

[42]  Andreina Santagostino,et al.  A User-Friendly Entry to 2-Iodoxybenzoic Acid (IBX) , 1999 .

[43]  Y. W. Andemichael,et al.  Improved Synthesis of Enantiopure Sulfinimines (Thiooxime S-Oxides) from p-Toluenesulfinamide and Aldehydes and Ketones , 1999 .

[44]  Yoshio Suzuki,et al.  Chiral β-phosphino sulfoxides as chiral ligands in palladium-catalyzed asymmetric allylic nucleophilic substitution reactions , 1999 .

[45]  A. Lorente,et al.  Enantiomerically pure 2-alkyl and 2,3-dialkylaziridines from 2-sulfinylimines , 1998 .

[46]  C. Crews,et al.  Synthesis of 9-fluorenylmethoxycarbonyl-protected amino aldehydes , 1998 .

[47]  Nan-Sheng Li,et al.  ASYMMETRIC SYNTHESIS OF ALKYLARYLCARBINOLS VIA REACTION OF A CHIRAL PINANEDIOL ALKYLBORONIC ESTER WITH ARYLMETHYL CHLORIDES , 1997 .

[48]  P. Wessig,et al.  A Convenient One-Pot Conversion of N-Boc-β-Aminoalcohols into N-Boc-Aziridines , 1997 .

[49]  D. Berta,et al.  Chiral sulfoxides and sulfides tethered to pyridines as ligands for enantioselective catalysis: Palladium catalyzed allylic substitution and addition of diethylzinc to benzaldehyde , 1997 .

[50]  and Ryoji Noyori,et al.  Asymmetric Transfer Hydrogenation Catalyzed by Chiral Ruthenium Complexes , 1997 .

[51]  M. Ordóñez,et al.  Enantioselective Diels-Alder reactions catalyzed by chiral magnesium lewis acids prepared from hydroxysulfoxides , 1996 .

[52]  P. Jadhav,et al.  Preparation and structure-activity relationship of novel P1/P1'-substituted cyclic urea-based human immunodeficiency virus type-1 protease inhibitors. , 1996, Journal of medicinal chemistry.

[53]  C. Tarnus,et al.  Difluoromethyleneketone retroamide, a versatile concept of inactivation of proteolytic enzymes , 1996 .

[54]  M. Sodeoka,et al.  Synthesis and crystal structure of a new c2-symmetric chiral bis-sulfoxide ligand and its palladium(ii) complex , 1995 .

[55]  A. Heitz,et al.  Improved solid phase synthesis of C-terminal peptide aldehydes , 1995 .

[56]  A. Alexakis,et al.  Chiral Aminal Templates - Diastereoselective Addition To Hydrazones - An Asymmetric-synthesis of Alpha-amino Aldehydes , 1995 .

[57]  J. Bower,et al.  Enantioselective palladium catalysed allylic substitution. Electronic and steric effects of the ligand. , 1994 .

[58]  M. Maestro,et al.  Catalytic activity of chiral β-hydroxysulfoxides in the enantioselective addition of diethylzinc to benzaldehyde. , 1993 .

[59]  N. Khiar,et al.  C2-Symmetric bis-sulfoxides as chiral ligands in metal catalysed asymmetric diels-alder reactions. , 1993 .

[60]  L. Hegedus,et al.  Synthesis of azapenams, diazepinones, and dioxocyclams via the photolytic reaction of chromium alkoxycarbene complexes with imidazolines , 1992 .

[61]  A. Konradi,et al.  Pinacol homocoupling of (S)-2-[N-(benzyloxycarbonyl)amino] aldehydes by [V2Cl3(THF)6]2[Zn2Cl6]. Synthesis of C2-symmetric (1S,2R,3R,4S)-1,4-diamino 2,3-diols , 1992 .

[62]  A. Heitz,et al.  A facile synthesis of chiral N-protected β-amino alcohols. , 1991 .

[63]  B. James,et al.  Enantioselective transfer hydrogenation of ketones using a rhodium catalyst containing a methionine sulphoxide ligand , 1986 .

[64]  C. Tamm,et al.  Approaches to the Synthesis of Cytochalasans. Part 4. Improved Synthesis of the Tetrahydroisoindoline Subunits Related to the Cytochalasins and Aspochalasins , 1983 .

[65]  R. Mcmillan,et al.  Catalytic asymmetric hydrogenation using ruthenium(II) complexes with chelating chiral sulfoxide ligands , 1977 .