Half-Sandwich Iridium Complexes for the One-Pot Synthesis of Amides: Preparation, Structure, and Diverse Catalytic Activity.

Several types of air-stable N,O-coordinate half-sandwich iridium complexes containing Schiff base ligands with the general formula [Cp*IrClL] were synthesized in good yields. These stable iridium complexes displayed a good catalytic efficiency in amide synthesis. A variety of amides with different substituents were obtained in a one-pot procedure with excellent yields and high selectivities through the amidation of aldehydes with NH2OH·HCl and nitrile hydration under the catalysis of complexes 1-4. The excellent and diverse catalytic activity, mild conditions, broad substance scope, and environmentally friendly solvent make this system potentially applicable in industrial production. Half-sandwich iridium complexes 1-4 were characterized by NMR, elemental analysis, and IR techniques. Molecular structures of complexes 2 and 3 were confirmed by single-crystal X-ray analysis.

[1]  M. Thirumal,et al.  Ruthenium(III) 2-(aminofluoreneazo)phenolate complexes: Synthesis, characterization, catalytic activity in amidation reaction and Fluorescence quenching studies , 2020 .

[2]  Yan Jin,et al.  Half-Sandwich Ruthenium Complexes for One-Pot Synthesis of Quinolines and Tetrahydroquinolines: Diverse Catalytic Activity in the Coupled Cyclization and Hydrogenation Process. , 2020, Inorganic chemistry.

[3]  R. Nandhini,et al.  Half-sandwich ruthenium(II) complexes containing biphenylamine based Schiff base ligands: Synthesis, structure and catalytic activity in amidation of various aldehydes , 2020 .

[4]  Zi‐Jian Yao,et al.  Air-Stable Half-Sandwich Iridium Complexes as Aerobic Oxidation Catalysts for Imine Synthesis. , 2020, Inorganic chemistry.

[5]  S. Bai,et al.  Self-Assembly, Structural Transformation and Guest-Binding Properties of Supramolecular Assemblies with Triangular Metal-Metal Bonded Units. , 2020, Journal of the American Chemical Society.

[6]  G. Venkatachalam,et al.  Half-sandwich Ruthenium(II) Schiff base complexes: Synthesis, characterization and effective catalysts for one-pot conversion of aldehydes to amides , 2019 .

[7]  F. Hahn,et al.  Supramolecular Control of Photocycloadditions in Solution: In Situ Stereoselective Synthesis and Release of Cyclobutanes. , 2019, Angewandte Chemie.

[8]  R. Joshi,et al.  (η6-Benzene)Ru(II) half-sandwich complexes of pyrazolated chalcogenoethers for catalytic activation of aldehydes to amides transformation , 2019, Journal of Organometallic Chemistry.

[9]  R. Grubbs,et al.  Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques. , 2018, Journal of the American Chemical Society.

[10]  Serkan Dayan,et al.  One-pot stepwise reductive amination reaction by N -coordinate sulfonamido-functionalized Ru(II) complexes in water , 2018, Applied Organometallic Chemistry.

[11]  Peng Li,et al.  Synthesis, structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes , 2018 .

[12]  B. Therrien,et al.  Strategies toward the Enhanced Permeability and Retention Effect by Increasing the Molecular Weight of Arene Ruthenium Metallaassemblies. , 2017, Inorganic chemistry.

[13]  P. Li,et al.  Mononuclear half-sandwich iridium and rhodium complexes through C‒H activation: Synthesis, characterization and catalytic activity , 2017 .

[14]  P. Boyle,et al.  Catalytic Acceptorless Dehydrogenation of Amines with Ru(PR2NR′2) and Ru(dppp) Complexes , 2017 .

[15]  Zhuqi Chen,et al.  Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature , 2017 .

[16]  Yuhong Wang,et al.  Synthesis, characterization and polymerization activity of copper complexes with N, O-chelate ligands , 2016 .

[17]  Qiang Wang,et al.  Soluble Metal-Nanoparticle-Decorated Porous Coordination Polymers for the Homogenization of Heterogeneous Catalysis. , 2016, Journal of the American Chemical Society.

[18]  P. Viswanathamurthi,et al.  Ruthenium(II) complexes incorporating salicylaldiminato-functionalized N-heterocyclic carbene ligands as efficient and versatile catalysts for hydration of organonitriles , 2016 .

[19]  M. Meyer,et al.  Trinuclear Half‐Sandwich RuII, RhIII and IrIII Polyester Organometallic Complexes: Synthesis and in vitro Evaluation as Antitumor Agents , 2015 .

[20]  T. Wirth,et al.  High-Temperature Synthesis of Amides from Alcohols or Aldehydes by Using Flow Chemistry , 2014 .

[21]  G. Jin,et al.  Half-sandwich iridium- and rhodium-based organometallic architectures: rational design, synthesis, characterization, and applications. , 2014, Accounts of chemical research.

[22]  G. Jin,et al.  Transition metal complexes based on carboranyl ligands containing N, P, and S donors: Synthesis, reactivity and applications , 2013 .

[23]  P. Štěpnička,et al.  Heterodinuclear Arene Ruthenium Complexes Containing a Glycine-Derived Phosphinoferrocene Carboxamide: Synthesis, Molecular Structure, Electrochemistry, and Catalytic Oxidation Activity in Aqueous Media , 2012 .

[24]  P. Sadler,et al.  Photoactivatable Organometallic Pyridyl Ruthenium(II) Arene Complexes , 2012 .

[25]  J. Bode,et al.  Rethinking amide bond synthesis , 2011, Nature.

[26]  A. Lapkin,et al.  Copper-catalyzed rearrangement of oximes into primary amides , 2011 .

[27]  D. Chakraborty,et al.  FeIII‐Catalyzed Synthesis of Primary Amides from Aldehydes , 2011 .

[28]  Tianfu Liu,et al.  Homochiral nickel coordination polymers based on salen(Ni) metalloligands: synthesis, structure, and catalytic alkene epoxidation. , 2011, Inorganic chemistry.

[29]  S. Marsden,et al.  Iridium-catalyzed formylation of amines with paraformaldehyde , 2010 .

[30]  S. Dabbs,et al.  Flexible palladium-catalysed amidation reactions for the synthesis of complex aryl amides , 2010 .

[31]  C. Allen,et al.  Cost efficient synthesis of amides from oximes with indium or zinc catalysts , 2010 .

[32]  R. Crabtree,et al.  A simple Ru catalyst for the conversion of aldehydes or oximes to primary amides , 2010 .

[33]  T. Punniyamurthy,et al.  Palladium-Catalyzed One-Pot Conversion of Aldehydes to Amides , 2010 .

[34]  S. Nolan,et al.  Au/Ag-cocatalyzed aldoximes to amides rearrangement under solvent- and acid-free conditions. , 2010, The Journal of organic chemistry.

[35]  Jinwoo Lee,et al.  Anhydrous hydration of nitriles to amides using aldoximes as the water source. , 2009, Organic letters.

[36]  G. Jin,et al.  Half-Sandwich Chromium(III) Catalysts Bearing Hydroxyindanimine Ligands for Ethylene Polymerization , 2009 .

[37]  M. Crestani,et al.  Catalytic hydration of mono and dinitriles using nickel(0) and PTSA , 2009 .

[38]  K. Endo,et al.  Rh(I)-catalyzed hydration of organonitriles under ambient conditions. , 2008, Angewandte Chemie.

[39]  Jonathan M. J. Williams,et al.  Iridium-catalyzed conversion of alcohols into amides via oximes. , 2007, Organic letters.

[40]  F. Verpoort,et al.  Ruthenium complexes bearing bidentate Schiff base ligands as efficient catalysts for organic and polymer syntheses , 2005 .

[41]  P. Sadler,et al.  Organometallic chemistry, biology and medicine: ruthenium arene anticancer complexes. , 2005, Chemical communications.

[42]  P. A. Vigato,et al.  The challenge of cyclic and acyclic schiff bases and related derivatives , 2004 .

[43]  Sukbok Chang,et al.  Rh-catalyzed one-pot and practical transformation of aldoximes to amides. , 2003, Chemical communications.

[44]  D. Atwood,et al.  Group 13 compounds incorporating Salen ligands. , 2001, Chemical reviews.

[45]  A. Chamberlin,et al.  Chemical Synthesis of Natural Product Peptides: Coupling Methods for the Incorporation of Noncoded Amino Acids into Peptides. , 1997, Chemical reviews.

[46]  L. Field,et al.  Isomerization of Aldoximes to Amides under Substantially Neutral Conditions1 , 1961 .

[47]  C. Hauser,et al.  DEHYDRATION OR BECKMANN REARRANGEMENT OF ALDOXIMES WITH BORON FLUORIDE. CONVERSION OF ALDOXIMES TO CORRESPONDING AMIDES , 1955 .