Ether-tethered Ru(II)/TsDPEN complexes; synthesis and applications to asymmetric transfer hydrogenation

A new type of Ru(II)/TsDPEN catalyst containing an ether-based linking tether has been prepared and shown to exhibit excellent activity in asymmetric transfer hydrogenation reactions of ketones. Related complexes containing a hydroxyl-terminated alkyl chain have also been prepared and tested as asymmetric catalysts. In some cases the activity of the new catalyst type complements that of the closely related alkyl-chain tethered complexes.

[1]  T. Ikariya,et al.  Oxo-tethered ruthenium(II) complex as a bifunctional catalyst for asymmetric transfer hydrogenation and H2 hydrogenation. , 2011, Journal of the American Chemical Society.

[2]  A. Chan,et al.  Highly enantioselective hydrogenation of quinolines using phosphine-free chiral cationic ruthenium catalysts: scope, mechanism, and origin of enantioselectivity. , 2011, Journal of the American Chemical Society.

[3]  Xingshu Li,et al.  The synthesis of a new nitrogen joined N-PEG-TsDPEN ligand and its application in asymmetric transfer hydrogenation of ketones in neat water , 2011 .

[4]  B. Sridhar,et al.  Enantioselective synthesis of cyclopropyl δ-lactonealdehydes and dodecyl-5-ene-1-yne-3-ol: advanced intermediates of solandelactone A and B , 2011 .

[5]  M. Wills,et al.  The importance of the N-H bond in Ru/TsDPEN complexes for asymmetric transfer hydrogenation of ketones and imines. , 2011, Organic & biomolecular chemistry.

[6]  Shane W. Krska,et al.  Highly enantioselective synthesis of anti aryl β-hydroxy α-amino esters via DKR transfer hydrogenation , 2011 .

[7]  Yawen Zhang,et al.  Highly enantioselective synthesis of β-hydroxysulfonamides by asymmetric transfer hydrogenation , 2011 .

[8]  P. A. Bradley,et al.  The Synthesis of Two Potent β-3 Adrenergic Receptor Agonists , 2010 .

[9]  M. Wills,et al.  Applications of N′-alkylated derivatives of TsDPEN in the asymmetric transfer hydrogenation of CO and CN bonds , 2010 .

[10]  G. Clarkson,et al.  Synthesis and use of a stable aminal derived from TsDPEN in asymmetric organocatalysis , 2010 .

[11]  A. D. Zotto,et al.  Chiral Pincer Ruthenium and Osmium Complexes for the Fast and Efficient Hydrogen Transfer Reduction of Ketones , 2010 .

[12]  M. Wills,et al.  Asymmetric transfer hydrogenation of quinolines using tethered Ru(II) catalysts , 2010 .

[13]  U. Urleb,et al.  Stereoselective synthesis of fluorine-containing analogues of anti-bacterial sanfetrinem and LK-157 , 2010 .

[14]  Yanmei He,et al.  Phosphine-free chiral metal catalysts for highly effective asymmetric catalytic hydrogenation. , 2010, Organic & biomolecular chemistry.

[15]  Masato M. Ito,et al.  Bifunctional Triflylamide-Tethered Cp′Rh and Cp′Ir Complexes: A New Entry for Asymmetric Hydrogenation Catalysts , 2010 .

[16]  Masato M. Ito,et al.  Synthesis and structure of protic amine tethered rhodium(III) peralkylcyclopentadienyl complexes , 2010 .

[17]  G. Clarkson,et al.  Kinetic and structural studies on 'tethered' Ru(II) arene ketone reduction catalysts. , 2010, Dalton transactions.

[18]  B. Sridhar,et al.  A flexible enantioselective total synthesis of diospongins A and B and their enantiomers using catalytic hetero-Diels-Alder/Rh-catalyzed 1,4-addition and asymmetric transfer hydrogenation reactions as key steps. , 2009, The Journal of organic chemistry.

[19]  L. Eriksson,et al.  Asymmetric transfer hydrogenation of ketones catalyzed by amino acid derived rhodium complexes: on the origin of enantioselectivity and enantioswitchability. , 2009, Chemistry.

[20]  Jian-Liang Ye,et al.  Asymmetric total synthesis of (-)-awajanomycin. , 2009, Organic letters.

[21]  M. Yus,et al.  Ruthenium-catalysed asymmetric transfer hydrogenation of N-(tert-butanesulfinyl)imines , 2009 .

[22]  Bo Zhang,et al.  Catalytic enantioselective synthesis of chiral phthalides by efficient reductive cyclization of 2-acylarylcarboxylates under aqueous transfer hydrogenation conditions. , 2009, Organic letters.

[23]  Jinlong Wu,et al.  Synthesis of the C1–C12 acid fragment of amphidinolide T marine macrolides via SmI2-mediated enantioselective reductive coupling of aldehydes with a chiral crotonate , 2009 .

[24]  Jianliang Xiao,et al.  pH-regulated asymmetric transfer hydrogenation of quinolines in water. , 2009, Angewandte Chemie.

[25]  Elina Buitrago,et al.  Mechanistic investigations into the asymmetric transfer hydrogenation of ketones catalyzed by pseudo-dipeptide ruthenium complexes. , 2009, Chemistry.

[26]  Jianliang Xiao,et al.  Metal-Brønsted acid cooperative catalysis for asymmetric reductive amination. , 2009, Journal of the American Chemical Society.

[27]  T. Rauchfuss,et al.  Proton-assisted activation of dihydrogen: mechanistic aspects of proton-catalyzed addition of H2 to Ru and Ir amido complexes. , 2009, Journal of the American Chemical Society.

[28]  Michael J. Hall,et al.  A convergent approach toward the C1-C11 subunit of phoslactomycins and formal synthesis of phoslactomycin B. , 2009, Organic letters.

[29]  G. Clarkson,et al.  Ru(II) complexes of N-alkylated TsDPEN ligands in asymmetric transfer hydrogenation of ketones and imines. , 2009, Organic letters.

[30]  Yawen Zhang,et al.  Dynamic kinetic resolution of beta-keto sulfones via asymmetric transfer hydrogenation. , 2009, Chemical communications.

[31]  T. Ikariya,et al.  Remarkable Positive Effect of Silver Salts on Asymmetric Hydrogenation of Acyclic Imines with Cp*Ir Complexes Bearing Chiral N-Sulfonylated Diamine Ligands , 2009 .

[32]  Lijin Xu,et al.  Air-stable and phosphine-free iridium catalysts for highly enantioselective hydrogenation of quinoline derivatives. , 2008, Organic letters.

[33]  Masato M. Ito,et al.  Well-Defined Triflylamide-Tethered Arene−Ru(Tsdpen) Complexes for Catalytic Asymmetric Hydrogenation of Ketones , 2008 .

[34]  A. Chan,et al.  Hydrogenation of quinolines using a recyclable phosphine-free chiral cationic ruthenium catalyst: enhancement of catalyst stability and selectivity in an ionic liquid. , 2008, Angewandte Chemie.

[35]  Jianliang Xiao,et al.  Chiral counteranion-aided asymmetric hydrogenation of acyclic imines. , 2008, Journal of the American Chemical Society.

[36]  Jianliang Xiao,et al.  Broader, greener, and more efficient: recent advances in asymmetric transfer hydrogenation. , 2008, Chemistry, an Asian journal.

[37]  Jianliang Xiao,et al.  Asymmetric hydrogenation of cyclic imines with an ionic Cp*Rh(III) catalyst. , 2008, Journal of the American Chemical Society.

[38]  M. Wills,et al.  Asymmetric transfer hydrogenation of C=O and C=N bonds by tethered Rh(III) catalysts. , 2008, Chemistry, an Asian journal.

[39]  D. Uemura,et al.  Stereocontrolled synthesis of the C79–C96 fragment of symbiodinolide , 2008 .

[40]  W. Woggon,et al.  Enantioselective Transfer Hydrogenation of Aliphatic Ketones Catalyzed by Ruthenium Complexes Linked to the Secondary Face of β-Cyclodextrin , 2008 .

[41]  T. Rauchfuss,et al.  Lewis base adducts derived from transfer hydrogenation catalysts: Scope and selectivity , 2008 .

[42]  Jianliang Xiao,et al.  Rh III- and Ir III-catalyzed asymmetric transfer hydrogenation of ketones in water. , 2008, Chemistry.

[43]  Masato M. Ito,et al.  Catalytic hydrogenation of polar organic functionalities based on Ru-mediated heterolytic dihydrogen cleavage. , 2007, Chemical communications.

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

[45]  D. Fox,et al.  An investigation into the tether length and substitution pattern of arene-substituted complexes for asymmetric transfer hydrogenation of ketones. , 2007, Organic letters.

[46]  T. Clark,et al.  Intramolecular trapping of an intermediate in the reduction of imines by a hydroxycyclopentadienyl ruthenium hydride: support for a concerted outer sphere mechanism. , 2007, Journal of the American Chemical Society.

[47]  Jianliang Xiao,et al.  Aqueous-phase asymmetric transfer hydrogenation of ketones--a greener approach to chiral alcohols. , 2007, Chemical communications.

[48]  T. Ohkuma,et al.  Asymmetric hydrogenation of alpha-hydroxy ketones catalyzed by MsDPEN-Cp*Ir(III) complex. , 2007, Organic letters.

[49]  M. Wills,et al.  The use of a [4 + 2] cycloaddition reaction for the preparation of a series of 'tethered' Ru(II)-diamine and aminoalcohol complexes. , 2007, Organic & biomolecular chemistry.

[50]  E. Meijer,et al.  Realistic modeling of ruthenium-catalyzed transfer hydrogenation. , 2007, Journal of the American Chemical Society.

[51]  R. Noyori,et al.  Asymmetric Hydrogenation of α-Chloro Aromatic Ketones Catalyzed by η6-Arene/TsDPEN−Ruthenium(II) Complexes , 2007 .

[52]  T. Ikariya,et al.  Synthesis and properties of alkylruthenium complexes bearing primary and secondary amine ligands , 2007 .

[53]  T. E. Cole,et al.  New C2-symmetric bis(sulfonamide)-cyclohexane-1,2-diamine-RhCp∗ complex and its application in the asymmetric transfer hydrogenation (ATH) of ketones in water , 2006 .

[54]  J. Bäckvall,et al.  Mechanistic study of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride. Experimental support for a mechanism involving coordination of imine to ruthenium prior to hydrogen transfer. , 2006, Journal of the American Chemical Society.

[55]  J. Bäckvall,et al.  Efficient ruthenium-catalyzed transfer hydrogenation/hydrogenation of 1,3-cycloalkanediones to 1,3-cycloalkanediols using microwave heating. , 2006, The Journal of organic chemistry.

[56]  T. Rauchfuss,et al.  Proton-induced lewis acidity of unsaturated iridium amides. , 2006, Journal of the American Chemical Society.

[57]  M. Wills,et al.  The "reverse-tethered" ruthenium (II) catalyst for asymmetric transfer hydrogenation: further applications. , 2006, The Journal of organic chemistry.

[58]  R. Noyori,et al.  Mechanism of asymmetric hydrogenation of acetophenone catalyzed by chiral eta(6)-arene-N-tosylethylenediamine-ruthenium(II) complexes. , 2006, Chemistry, an Asian journal.

[59]  J. Bäckvall,et al.  Mechanistic investigation on the hydrogenation of imines by[p-(Me2CH)C6H4Me]RuH(NH2CHPhCHPhNSO2C6H4-p-CH3). Experimental support for an ionic pathway. , 2006, Chemical communications.

[60]  R. Noyori,et al.  The hydrogenation/transfer hydrogenation network: asymmetric hydrogenation of ketones with chiral eta6-arene/N-Tosylethylenediamine-ruthenium(II) catalysts. , 2006, Journal of the American Chemical Society.

[61]  D. Blackmond,et al.  Kinetic Studies of the Asymmetric Transfer Hydrogenation of Imines with Formic Acid Catalyzed by Rh−Diamine Catalysts , 2006 .

[62]  P. Andersson,et al.  Mechanistic aspects of transition metal-catalyzed hydrogen transfer reactions. , 2006, Chemical Society reviews.

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

[64]  M. Wills,et al.  Asymmetric transfer hydrogenation of a,-unsaturated, a-tosyloxy and a-substituted ketones , 2006 .

[65]  T. Ikariya,et al.  Bifunctional transition metal-based molecular catalysts for asymmetric syntheses. , 2006, Organic & biomolecular chemistry.

[66]  G. Clarkson,et al.  A stereochemically well-defined rhodium(III) catalyst for asymmetric transfer hydrogenation of ketones. , 2005, Organic letters.

[67]  M. Wills,et al.  One-pot formation of nitrogen-containing heterocyclic ring systems using a deprotection-cyclisation-asymmetric reduction sequence. , 2005, Chemical communications.

[68]  T. Ikariya,et al.  A remarkably effective catalyst for the asymmetric transfer hydrogenation of aromatic ketones in water and air. , 2005, Chemical communications.

[69]  Jianliang Xiao,et al.  Insight into and practical application of pH-controlled asymmetric transfer hydrogenation of aromatic ketones in water. , 2005, Angewandte Chemie.

[70]  G. Clarkson,et al.  A class of ruthenium(II) catalyst for asymmetric transfer hydrogenations of ketones. , 2005, Journal of the American Chemical Society.

[71]  D. Xue,et al.  Transfer hydrogenation of activated C=C bonds catalyzed by ruthenium amido complexes: reaction scope, limitation, and enantioselectivity. , 2005, The Journal of organic chemistry.

[72]  Iwao Ojima,et al.  Catalytic Asymmetric Synthesis: Ojima/Asymmetric Synthesis , 2005 .

[73]  J. B. Johnson,et al.  Isomerization and deuterium scrambling evidence for a change in the rate-limiting step during imine hydrogenation by Shvo's hydroxycyclopentadienyl ruthenium hydride. , 2005, Journal of the American Chemical Society.

[74]  I. Lennon,et al.  An efficient catalytic asymmetric route to 1-aryl-2-imidazol-1-yl-ethanols , 2005 .

[75]  R. Morris,et al.  Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes , 2004 .

[76]  M. Mogi,et al.  Asymmetric reduction of methoxy substituted β-tetralones using transfer hydrogenation , 2004 .

[77]  A. Gavriilidis,et al.  Asymmetric Transfer Hydrogenation of Acetophenone with 1R,2S-Aminoindanol/Pentamethylcyclopentadienylrhodium Catalyst , 2004 .

[78]  T. Ikariya,et al.  A practical synthesis of optically active aromatic epoxides via asymmetric transfer hydrogenation of α-chlorinated ketones with chiral rhodium–diamine catalyst , 2004 .

[79]  P. Andersson,et al.  Origin of enantioselectivity in the Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones. , 2004, The Journal of organic chemistry.

[80]  P. Dyson,et al.  A versatile ruthenium precursor for biphasic catalysis and its application in ionic liquid biphasic transfer hydrogenation: conventional vs task-specific catalysts. , 2004, Journal of the American Chemical Society.

[81]  Juliette Martin,et al.  Scale‐Up Studies in Asymmetric Transfer Hydrogenation , 2004 .

[82]  G. Clarkson,et al.  A new class of "tethered" ruthenium(II) catalyst for asymmetric transfer hydrogenation reactions. , 2004, Journal of the American Chemical Society.

[83]  T. Ikariya,et al.  Mechanistic Aspects of Formation of Chiral Ruthenium Hydride Complexes from 16‐Electron Ruthenium Amide Complexes and Formic Acid: Facile Reversible Decarboxylation and Carboxylation , 2004 .

[84]  R. Pike,et al.  A one-pot process for the enantioselective synthesis of amines via reductive amination under transfer hydrogenation conditions. , 2003, Organic letters.

[85]  Adam L. Sisson,et al.  Functionalized-arene ruthenium half-sandwich compounds as enantioselective hydrogen transfer catalysts. Crystal structures of [RuCl{TsNCH(R)CH(R)NH2}(η6-C6H5OCH2CH2OH)] (R=H or Ph) , 2003 .

[86]  J. B. Johnson,et al.  Kinetic isotope effect evidence for a concerted hydrogen transfer mechanism in transfer hydrogenations catalyzed by [p-(Me2CH)C6H4Me]Ru- (NHCHPhCHPhNSO2C6H4-p-CH3). , 2003, The Journal of organic chemistry.

[87]  B. Mohar,et al.  New chiral N-(N,N-dialkylamino)sulfamoyl-1,2-diamine ligands for highly enantioselective transfer hydrogenation of ketones , 2002 .

[88]  M. Wills,et al.  Dynamic kinetic resolution–asymmetric transfer hydrogenation of 1-aryl-substituted cyclic ketones , 2002 .

[89]  T. Ikariya,et al.  Practical synthesis of optically active styrene oxides via reductive transformation of 2-chloroacetophenones with chiral rhodium catalysts. , 2002, Organic letters.

[90]  Ryoji Noyori,et al.  Asymmetric catalysis: science and opportunities (Nobel lecture). , 2002, Angewandte Chemie.

[91]  R. Noyori,et al.  Metal-ligand bifunctional catalysis: a nonclassical mechanism for asymmetric hydrogen transfer between alcohols and carbonyl compounds. , 2001, The Journal of organic chemistry.

[92]  R. Noyori,et al.  CH/π Attraction: The Origin of Enantioselectivity in Transfer Hydrogenation of Aromatic Carbonyl Compounds Catalyzed by Chiral η6 -Arene-Ruthenium(II) Complexes. , 2001, Angewandte Chemie.

[93]  M. Wills,et al.  Rhodium versus ruthenium: contrasting behaviour in the asymmetric transfer hydrogenation of α-substituted acetophenones , 2001 .

[94]  S. Brown,et al.  Efficient rhodium and iridium-catalysed asymmetric transfer hydrogenation using water-soluble aminosulfonamide ligands , 2001 .

[95]  T. Ikariya,et al.  Stereoselective synthesis of optically active pyridyl alcohols via asymmetric transfer hydrogenation of pyridyl ketones , 2000 .

[96]  T. Ikariya,et al.  Stereoselective synthesis of optically active alpha-hydroxy ketones and anti-1,2-diols via asymmetric transfer hydrogenation of unsymmetrically substituted 1,2-diketones. , 2000, Organic letters.

[97]  A. Collet,et al.  Practical Synthesis of (S)-1-(3-Trifluoromethylphenyl)ethanol via Ruthenium(II)-catalyzed Asymmetric Transfer Hydrogenation , 2000 .

[98]  M. Hennig,et al.  Synthesis of (R)- and (S)-4-hydroxyisophorone by ruthenium-catalyzed asymmetric transfer hydrogenation of ketoisophorone , 2000 .

[99]  Ryoji Noyori,et al.  The Metal−Ligand Bifunctional Catalysis: A Theoretical Study on the Ruthenium(II)-Catalyzed Hydrogen Transfer between Alcohols and Carbonyl Compounds , 2000 .

[100]  P. Andersson,et al.  Ru(arene)(amino alcohol)-Catalyzed Transfer Hydrogenation of Ketones: Mechanism and Origin of Enantioselectivity , 1999 .

[101]  T. Ikariya,et al.  A Practical Stereoselective Synthesis of Chiral Hydrobenzoins via Asymmetric Transfer Hydrogenation of Benzils , 1999 .

[102]  D. Baker,et al.  A chiral rhodium complex for rapid asymmetric transfer hydrogenation of imines with high enantioselectivity. , 1999, Organic letters.

[103]  M. Wills,et al.  Asymmetric transfer hydrogenation of C=O and C=N bonds , 1999 .

[104]  V. Caprio,et al.  Catalysis in Asymmetric Synthesis , 1999 .

[105]  E. Jacobsen,et al.  Comprehensive Asymmetric Catalysis I–III , 1999 .

[106]  T. Ikariya,et al.  Asymmetric Transfer Hydrogenation of a,-Acetylenic Ketones , 1997 .

[107]  T. Ikariya,et al.  The Catalyst Precursor, Catalyst, and Intermediate in the RuII‐Promoted Asymmetric Hydrogen Transfer between Alcohols and Ketones , 1997 .

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

[109]  David A. Fletcher,et al.  The United Kingdom Chemical Database Service , 1996, J. Chem. Inf. Comput. Sci..

[110]  T. Ikariya,et al.  Asymmetric Transfer Hydrogenation of Imines , 1996 .

[111]  R. Noyori,et al.  Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using a Formic Acid−Triethylamine Mixture , 1996 .

[112]  T. Ikariya,et al.  Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes , 1995 .

[113]  R. Noyori,et al.  Asymmetric catalysis in organic synthesis , 1994 .

[114]  I. Ojima,et al.  Catalytic Asymmetric Synthesis , 1993 .