A Highly Selective Manganese-Catalyzed Synthesis of Imines under Phosphine-Free Conditions

An efficient and highly selective phosphine-free NN-manganese(I) complex catalyst system was developed for the acceptorless dehydrogenative coupling of alcohols with amines to form imines. The coupling reactions underwent at 3 mol % catalyst loading, and a large range of alcohols and amines with diverse functional groups was applied, including challenging diol and diamine. The target imine products were obtained in good to excellent yields. The present work provides an alternative method to construct highly active nonprecious metal complex catalysts based on phosphine-free ligands.

[1]  D. Procter,et al.  Copper-Catalyzed Borylative Multicomponent Synthesis of Quaternary α-Amino Esters , 2019, ACS Catalysis.

[2]  R. Kempe,et al.  3d-Metal Catalyzed N- and C-Alkylation Reactions via Borrowing Hydrogen or Hydrogen Autotransfer. , 2018, Chemical reviews.

[3]  D. Milstein,et al.  Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes , 2018, ACS Catalysis.

[4]  R. Kempe,et al.  Manganese-Catalyzed and Base-Switchable Synthesis of Amines or Imines via Borrowing Hydrogen or Dehydrogenative Condensation , 2018, ACS Catalysis.

[5]  Tingting Liu,et al.  Manganese-Catalyzed β-Alkylation of Secondary Alcohols with Primary Alcohols under Phosphine-Free Conditions , 2018, ACS Catalysis.

[6]  R. Kempe,et al.  Manganese Complexes for (De)Hydrogenation Catalysis: A Comparison to Cobalt and Iron Catalysts. , 2018, Angewandte Chemie.

[7]  Jun Guo,et al.  Cobalt-Catalyzed Asymmetric Sequential Hydroboration/Hydrogenation of Internal Alkynes. , 2017, Journal of the American Chemical Society.

[8]  Xin Hong,et al.  Iron-Catalyzed Hydroboration of Vinylcyclopropanes. , 2017, Organic letters.

[9]  Tingting Liu,et al.  NHTs Effect on the Enantioselectivity of Ru(II) Complex Catalysts Bearing a Chiral Bis(NHTs)-Substituted Imidazolyl-Oxazolinyl-Pyridine Ligand for Asymmetric Transfer Hydrogenation of Ketones , 2017 .

[10]  Miguel A. Esteruelas,et al.  Osmium hydride acetylacetonate complexes and their application in acceptorless dehydrogenative coupling of alcohols and amines and for the dehydrogenation of cyclic amines , 2017 .

[11]  M. Zirak,et al.  α-Imino Esters in Organic Synthesis: Recent Advances. , 2017, Chemical reviews.

[12]  G. Allmaier,et al.  Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride Mn(I) and Fe(II) PNP Pincer Complexes. , 2016, Chemistry.

[13]  L. Shimon,et al.  Manganese-Catalyzed Environmentally Benign Dehydrogenative Coupling of Alcohols and Amines to Form Aldimines and H2: A Catalytic and Mechanistic Study. , 2016, Journal of the American Chemical Society.

[14]  Jean Rodriguez,et al.  A Step into an eco-Compatible Future: Iron- and Cobalt-catalyzed Borrowing Hydrogen Transformation. , 2016, ChemSusChem.

[15]  T. Zell,et al.  Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization. , 2015, Accounts of chemical research.

[16]  Y. Obora Recent Advances in α-Alkylation Reactions using Alcohols with Hydrogen Borrowing Methodologies , 2014 .

[17]  M. Brimble,et al.  C-H functionalization in the synthesis of amino acids and peptides. , 2014, Chemical reviews.

[18]  S. Chakraborty,et al.  Iron-based catalysts for the hydrogenation of esters to alcohols. , 2014, Journal of the American Chemical Society.

[19]  B. Saha,et al.  Metal-ligand cooperation on a diruthenium platform: selective imine formation through acceptorless dehydrogenative coupling of alcohols with amines. , 2014, Chemistry.

[20]  P. Toy,et al.  Self-Supported Ligands as a Platform for Catalysis: Use of a Polymeric Oxime in a Recyclable Palladacycle Precatalyst for Suzuki–Miyaura Reactions , 2014 .

[21]  D. Milstein,et al.  Applications of Acceptorless Dehydrogenation and Related Transformations in Chemical Synthesis , 2013, Science.

[22]  L. Vaccaro,et al.  Bifunctional Ruthenium(II) PCP Pincer Complexes and Their Catalytic Activity in Acceptorless Dehydrogenative Reactions , 2013 .

[23]  Ping Wu,et al.  Ruthenium(II) Complex Catalysts Bearing a Pyridyl-Based Benzimidazolyl−Benzotriazolyl Ligand for Transfer Hydrogenation of Ketones , 2013 .

[24]  Y. Nakajima,et al.  Synthesis, Structures, and Reactivity of Ruthenium Complexes with PNP-pincer Type Phosphaalkene Ligands , 2013 .

[25]  SharmaUpendra,et al.  Highly efficient iron phthalocyanine catalyzed oxidative synthesis of imines from alcohols and amines , 2013 .

[26]  K. Ding,et al.  The N-H functional group in organometallic catalysis. , 2013, Angewandte Chemie.

[27]  Yehoshoa Ben‐David,et al.  Direct synthesis of pyrroles by dehydrogenative coupling of β-aminoalcohols with secondary alcohols catalyzed by ruthenium pincer complexes. , 2013, Angewandte Chemie.

[28]  S. Hanson,et al.  Cobalt-catalyzed acceptorless alcohol dehydrogenation: synthesis of imines from alcohols and amines. , 2013, Organic letters.

[29]  Weiwei Jin,et al.  A Highly Active Ruthenium(II) Pyrazolyl–Pyridyl–Pyrazole Complex Catalyst for Transfer Hydrogenation of Ketones , 2012 .

[30]  X. Pannecoucke,et al.  Ruthenium-catalyzed redox isomerization of trifluoromethylated allylic alcohols: mechanistic evidence for an enantiospecific pathway. , 2012, Angewandte Chemie.

[31]  Neeraj Kumar,et al.  Grafting of oxo-vanadium Schiff base on graphene nanosheets and its catalytic activity for the oxidation of alcohols , 2012 .

[32]  J. Schomaker,et al.  α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines. , 2012, Organic & biomolecular chemistry.

[33]  R. Madsen,et al.  Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex , 2012 .

[34]  S. A. Pullarkat,et al.  Efficient Iridium-Thioether-Dithiolate Catalyst for β-Alkylation of Alcohols and Selective Imine Formation via N-Alkylation Reactions , 2011 .

[35]  D. Milstein,et al.  Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and "green" catalysis. , 2011, Accounts of chemical research.

[36]  Timothy J. Wright,et al.  Reaction development and mechanistic study of a ruthenium catalyzed intramolecular asymmetric reductive amination en route to the dual Orexin inhibitor Suvorexant (MK-4305). , 2011, Journal of the American Chemical Society.

[37]  Miguel A. Esteruelas,et al.  Direct Access to POP-Type Osmium(II) and Osmium(IV) Complexes: Osmium a Promising Alternative to Ruthenium for the Synthesis of Imines from Alcohols and Amines , 2011 .

[38]  A. Goldman,et al.  Dehydrogenation and related reactions catalyzed by iridium pincer complexes. , 2011, Chemical reviews.

[39]  Y. Mu,et al.  Pincer Chromium(II) and Chromium(III) Complexes Supported by Bis(imino)aryl NCN ligands: Synthesis and Catalysis on Isoprene Polymerization , 2011 .

[40]  G. Huber,et al.  Renewable Chemical Commodity Feedstocks from Integrated Catalytic Processing of Pyrolysis Oils , 2010, Science.

[41]  M. Yus,et al.  Hydrogen autotransfer in the N-alkylation of amines and related compounds using alcohols and amines as electrophiles. , 2010, Chemical reviews.

[42]  D. Milstein,et al.  Direct synthesis of imines from alcohols and amines with liberation of H2. , 2010, Angewandte Chemie.

[43]  Zhengkun Yu,et al.  Construction of Highly Active Ruthenium(II) NNN Complex Catalysts Bearing a Pyridyl-Supported Pyrazolyl-Imidazolyl Ligand for Transfer Hydrogenation of Ketones , 2009 .

[44]  Z. Rappoport,et al.  The chemistry of hydroxylamines, oximes and hydroxamic acids , 2009 .

[45]  Dongmei Cui,et al.  Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichloride precursors. , 2008, Journal of the American Chemical Society.

[46]  A. Spek,et al.  trans-Arylplatinum(II) methyl compounds containing a bis(imino)aryl [NCN] ligand , 2004 .

[47]  A. Spek,et al.  New cis- and trans-Arylplatinum(II) Acetylide Compounds Containing a Bis(imino)aryl [NCN] Ligand , 2001 .