Iridium-Catalyzed Transfer Hydrogenation of 1,10-Phenanthrolines using Formic Acid as the Hydrogen Source

The iridium-catalyzed highly regioselective transfer hydrogenation of a variety of 2-substituted and 2,9-disubstituted 1,10-phenanthrolines under mild conditions with formic acid as the hydrogen source is described. In the presence of a catalytic amount of the iridium complex [Cp*IrCl2]2, the transfer hydrogenation proceeded smoothly in 1,4-dioxane under ligand-free conditions, exclusively leading to a range of 1,2,3,4-tetrahydro-1,10-phenanthroline products in high yields. The catalyst generated in situ from [Cp*IrCl2]2 and (R,R)-(CF3)2C6H3SO2-dpen [N-(2-amino-1,2-diphenylethyl)-3,5-bis(trifluoromethyl)benzenesulfonamide] could efficiently catalyze the asymmetric transfer hydrogenation of these 1,10-phenanthrolines in isopropyl alcohol (i-PrOH) to afford chiral 1,2,3,4-tetrahydro-1,10-phenanthrolines in high yields with up to >99% ee. The key to the success of the reduction is the choice of solvent and hydrogen source.

[1]  Lijin Xu,et al.  Versatile (Pentamethylcyclopentadienyl)rhodium‐2,2′‐Bipyridine (Cp*Rh‐bpy) Catalyst for Transfer Hydrogenation of N‐Heterocycles in Water , 2015 .

[2]  A. Vidal‐Ferran,et al.  Substrate Activation in the Catalytic Asymmetric Hydrogenation of N‐Heteroarenes , 2015 .

[3]  A. Herman,et al.  Molecular geometry and optical activity of helically chiral N-nitrosamines derived from 1,2,3,4-tetrahydro- and 1,2,3,4,7,8,9,10-octahydro-1,10-phenanthroline , 2015 .

[4]  Dong Wang,et al.  The golden age of transfer hydrogenation. , 2015, Chemical reviews.

[5]  Jianliang Xiao,et al.  Transfer hydrogenation in aqueous media , 2015 .

[6]  Anuja Joseph,et al.  Asymmetric Transfer Hydrogenation of Imines in Water by Varying the Ratio of Formic Acid to Triethylamine. , 2015, Organic letters.

[7]  Jianliang Xiao,et al.  A simple iridicycle catalyst for efficient transfer hydrogenation of N-heterocycles in water. , 2015, Chemistry.

[8]  Junseong Lee,et al.  Preparation of octahydro- and tetrahydro-[1,10]phenanthroline zirconium and hafnium complexes for olefin polymerization. , 2015, Dalton transactions.

[9]  Yanmei He,et al.  Advances in Transfer Hydrogenation of Carbonyl Compounds in Water , 2015 .

[10]  Bukuo Ni,et al.  Imidazolium ion tethered TsDPENs as efficient water-soluble ligands for rhodium catalyzed asymmetric transfer hydrogenation of aromatic ketones , 2014 .

[11]  Jianliang Xiao,et al.  Versatile iridicycle catalysts for highly efficient and chemoselective transfer hydrogenation of carbonyl compounds in water. , 2014, Chemistry.

[12]  M. Peruzzini,et al.  Transfer hydrogenation of ketones catalyzed by surface-active ruthenium and rhodium complexes in water. , 2014, Chemistry.

[13]  A. Herman,et al.  Helicity discrimination in N,N'-dibenzoyl-1,2,3,4,7,8,9,10-octahydro-1,10-phenanthrolines and their thiono- and selenocarbonyl analogues by inclusion complexation with chiral diols. , 2013, Organic & biomolecular chemistry.

[14]  Jian‐mei Lu,et al.  Reversible Hydrogenation–Oxidative Dehydrogenation of Quinolines over a Highly Active Pt Nanowire Catalyst under Mild Conditions , 2013 .

[15]  Jianliang Xiao,et al.  Robust cyclometallated Ir(III) catalysts for the homogeneous hydrogenation of N-heterocycles under mild conditions. , 2013, Chemical communications.

[16]  J. Qin,et al.  Asymmetric ruthenium-catalyzed hydrogenation of 2- and 2,9-substituted 1,10-phenanthrolines. , 2013, Angewandte Chemie.

[17]  Jianliang Xiao,et al.  Highly efficient transformation of levulinic acid into pyrrolidinones by iridium catalysed transfer hydrogenation. , 2013, Chemical communications.

[18]  Jianliang Xiao,et al.  Fast reductive amination by transfer hydrogenation "on water". , 2013, Chemistry.

[19]  Jianliang Xiao,et al.  Cyclometalated iridium complexes for transfer hydrogenation of carbonyl groups in water , 2013 .

[20]  Jianliang Xiao,et al.  Efficient and Chemoselective Reduction of Pyridines to Tetrahydropyridines and Piperidines via Rhodium-Catalyzed Transfer Hydrogenation , 2013 .

[21]  Liangchun Li,et al.  Chiral surfactant-type catalyst for asymmetric reduction of aliphatic ketones in water. , 2012, Journal of the American Chemical Society.

[22]  Jianliang Xiao,et al.  The remarkable effect of a simple ion: iodide-promoted transfer hydrogenation of heteroaromatics. , 2012, Chemistry.

[23]  Zhengkun Yu,et al.  Brønsted‐Säure‐Aktivierung bei der übergangsmetallkatalysierten asymmetrischen Hydrierung N‐ungeschützter Imine, Enamine und N‐Heteroarene , 2012 .

[24]  Weiwei Jin,et al.  Brønsted acid activation strategy in transition-metal catalyzed asymmetric hydrogenation of N-unprotected imines, enamines, and N-heteroaromatic compounds. , 2012, Angewandte Chemie.

[25]  William J. W. Watson,et al.  How do the fine chemical, pharmaceutical, and related industries approach green chemistry and sustainability? , 2012 .

[26]  Lijin Xu,et al.  Asymmetric hydrogenation of 2- and 2,3-substituted quinoxalines with chiral cationic ruthenium diamine catalysts. , 2011, Organic letters.

[27]  Jianliang Xiao,et al.  pH-Regulated transfer hydrogenation of quinoxalines with a Cp*Ir–diamine catalyst in aqueous media , 2011 .

[28]  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.

[29]  A. Chan,et al.  Highly efficient and enantioselective hydrogenation of quinolines and pyridines with Ir-Difluorphos catalyst. , 2010, Organic & biomolecular chemistry.

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

[31]  C. Len,et al.  Suzuki-Miyaura cross-coupling reactions in aqueous media: green and sustainable syntheses of biaryls. , 2010, ChemSusChem.

[32]  A. Chan,et al.  Highly Enantioselective Hydrogenation of Quinoline and Pyridine Derivatives with Iridium‐(P‐Phos) Catalyst , 2010 .

[33]  S. Jenkinson,et al.  Synthesis of a novel tricyclic 1,2,3,4,4a,5,6,10b-octahydro-1,10-phenanthroline ring system and CXCR4 antagonists with potent activity against HIV-1. , 2010, Bioorganic & medicinal chemistry letters.

[34]  R. Poli,et al.  Asymmetric hydrosilylation, transfer hydrogenation and hydrogenation of ketones catalyzed by iridium complexes , 2010 .

[35]  F. Felpin,et al.  Recyclable Heterogeneous Palladium Catalysts in Pure Water: Sustainable Developments in Suzuki, Heck, Sonogashira and Tsuji–Trost Reactions , 2010 .

[36]  Jianliang Xiao,et al.  Asymmetric Transfer Hydrogenation in Water with Platinum Group Metal Catalysts , 2010 .

[37]  C. Schneider,et al.  Enantioselective Synthesis of a Novel Chiral 2,9‐Disubstituted 1,10‐Phenanthroline and First Applications in Asymmetric Catalysis , 2009 .

[38]  A. Chan,et al.  Asymmetric hydrogenation of quinoxalines with diphosphinite ligands: a practical synthesis of enantioenriched, substituted tetrahydroquinoxalines. , 2009, Angewandte Chemie.

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

[40]  C. Metallinos,et al.  Neutral and Cationic Iridium(I) Complexes Bearing Chiral Phenanthroline-Derived Benzimidazolylidenes: Synthetic, Structural, and Catalytic Studies , 2009 .

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

[42]  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.

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

[44]  F. Vizza,et al.  Selective hydrogenation of 1.10-phenanthrolines by silica-supported palladium nanoparticles , 2008 .

[45]  Scott J. Miller,et al.  Selective partial reduction of quinolines: Hydrosilylation vs. transfer hydrogenation , 2008 .

[46]  Shufen Xu,et al.  Brønsted Acid Catalyzed Asymmetric Reduction of 2- and 2,9-Substituted 1,10-Phenanthrolines , 2008 .

[47]  J. Neudörfl,et al.  On the quantitative recycling of Raney–Nickel catalysts on a lab-scale , 2007 .

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

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

[50]  A. Chan,et al.  Asymmetric hydrogenation of quinolines with high substrate/catalyst ratio. , 2007, Chemical communications.

[51]  N. Taylor,et al.  Reduction of substituted 1,10-phenanthrolines as a route to rigid chiral benzimidazolylidenes , 2006 .

[52]  P. Frediani,et al.  Quinoline transfer hydrogenation by a rhodium bipyridine catalyst , 2006 .

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

[54]  A. Chan,et al.  Highly Enantioselective Iridium-Catalyzed Hydrogenation of Quinoline Derivatives Using Chiral Phosphinite H8-BINAPO , 2005 .

[55]  Chao-Jun Li,et al.  Organic reactions in aqueous media with a focus on carbon-carbon bond formations: a decade update. , 2005, Chemical reviews.

[56]  A. Chan,et al.  Air-stable Ir-(P-Phos) complex for highly enantioselective hydrogenation of quinolines and their immobilization in poly(ethylene glycol) dimethyl ether (DMPEG). , 2005, Chemical communications.

[57]  V. Derdau.  Deuterated ammonium formate as deuterium source in a mild catalytic deuterium transfer reaction of pyridines, pyrazines and isoquinolines , 2004 .

[58]  C. Metallinos,et al.  A benzimidazole-based N-heterocyclic carbene derived from 1,10-phenanthroline. , 2004, Organic letters.

[59]  K. Fujita,et al.  Regio- and chemoselective transfer hydrogenation of quinolines catalyzed by a Cp∗Ir complex , 2004 .

[60]  A. Mortreux,et al.  Ruthenium(II)‐Catalyzed Asymmetric Transfer Hydrogenation of Carbonyl Compounds with 2‐Propanol and Ephedrine‐Type Ligands. , 2003 .

[61]  Giorgio Chelucci,et al.  Chiral 2,2'-bipyridines, 1,10-phenanthrolines, and 2,2':6',2' '-terpyridines: syntheses and applications in asymmetric homogeneous catalysis. , 2002, Chemical reviews.

[62]  Chao‐Jun Li.  Quasi-nature catalysis: developing C-C bond formations catalyzed by late transition metals in air and water. , 2002, Accounts of chemical research.

[63]  C. Dockendorff,et al.  A mild procedure for the reduction of pyridine N-oxides to piperidines using ammonium formate. , 2001, The Journal of organic chemistry.

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

[65]  A. Srikrishna,et al.  Reduction of quinolines to 1,2,3,4-tetrahydro derivatives employing a combination of NaCNBH3 and BF3.OEt2 , 1996 .

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

[67]  J. Joule,et al.  A Novel Application of Ammonium Formate/Palladium on Carbon for Selective Reduction of the Heterocyclic Ring in Quinolines and Isoquinolines , 1990 .

[68]  R. Johnstone,et al.  Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds , 1985 .

[69]  Yoshihisa Watanabe,et al.  Ruthenium Catalyzed Reduction of Nitroarenes and Azaaromatic Compounds Using Formic Acid , 1984 .

[70]  R. L. Marks,et al.  Reactions of diborane with aromatic heterocycles—21 , 1983 .

[71]  L. A. Summers,et al.  Hydrogenation of 1,10-phenanthroline , 1975 .

[72]  T. Nestrick,et al.  Catalytic Transfer Hydrogenation , 1974 .