Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block.

This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.

[1]  R. Kempe,et al.  Cobalt-Catalyzed Alkylation of Secondary Alcohols with Primary Alcohols via Borrowing Hydrogen/Hydrogen Autotransfer. , 2017, Chemistry.

[2]  B. Stöger,et al.  Enantioselective Transfer Hydrogenation of Ketones Catalyzed by a Manganese Complex Containing an Unsymmetrical Chiral PNP′ Tridentate Ligand , 2017 .

[3]  R. Kempe,et al.  Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols. , 2017, Angewandte Chemie.

[4]  G. J. Harkness,et al.  A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation. , 2017, Angewandte Chemie.

[5]  L. Shimon,et al.  Manganese-Catalyzed Hydrogenation of Esters to Alcohols. , 2017, Chemistry.

[6]  M. Beller,et al.  Improved and General Manganese-Catalyzed N-Methylation of Aromatic Amines Using Methanol. , 2017, Chemistry.

[7]  Y. Diskin‐Posner,et al.  Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2 : A Catalytic and Mechanistic Study. , 2017, Angewandte Chemie.

[8]  T. Roisnel,et al.  Hydrogenation of ketones with a manganese PN3P pincer pre-catalyst , 2017 .

[9]  Veronica Papa,et al.  Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese–PNN pincer complex† †Electronic supplementary information (ESI) available: General experimental procedures, additional schemes and figures, characterization data and NMR spectra are available. See D , 2017, Chemical science.

[10]  Soon Hyeok Hong,et al.  Ruthenium-Catalyzed Aminomethylation and Methylation of Phenol Derivatives Utilizing Methanol as the C1 Source , 2017 .

[11]  V. Dorcet,et al.  Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex , 2017 .

[12]  F. Dumeignil,et al.  Manganese Pincer Complexes for the Base-Free, Acceptorless Dehydrogenative Coupling of Alcohols to Esters: Development, Scope, and Understanding , 2017 .

[13]  R. Kempe,et al.  Manganese-Catalyzed Multicomponent Synthesis of Pyrimidines from Alcohols and Amidines. , 2017, Angewandte Chemie.

[14]  M. Beller,et al.  Molecularly Defined Manganese Pincer Complexes for Selective Transfer Hydrogenation of Ketones. , 2017, ChemSusChem.

[15]  R. Ludwig,et al.  A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol , 2016, Angewandte Chemie.

[16]  M. Beller,et al.  Hydrogenation of Esters to Alcohols Catalyzed by Defined Manganese Pincer Complexes. , 2016, Angewandte Chemie.

[17]  G. Allmaier,et al.  Sustainable Synthesis of Quinolines and Pyrimidines Catalyzed by Manganese PNP Pincer Complexes. , 2016, Journal of the American Chemical Society.

[18]  Miguel Peña‐López,et al.  Manganese-Catalyzed Hydrogen-Autotransfer C-C Bond Formation: α-Alkylation of Ketones with Primary Alcohols. , 2016, Angewandte Chemie.

[19]  Matthias Beller,et al.  Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes , 2016, Nature Communications.

[20]  T. Dietel,et al.  Highly Active and Selective Manganese C=O Bond Hydrogenation Catalysts: The Importance of the Multidentate Ligand, the Ancillary Ligands, and the Oxidation State. , 2016, Angewandte Chemie.

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

[22]  R. Kempe,et al.  General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols. , 2016, Journal of the American Chemical Society.

[23]  Stephen P. Thomas,et al.  Recent Advances of Manganese Catalysis for Organic Synthesis , 2016 .

[24]  R. Ludwig,et al.  Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes. , 2016, Journal of the American Chemical Society.

[25]  G. Allmaier,et al.  Co(II) PCP Pincer Complexes as Catalysts for the Alkylation of Aromatic Amines with Primary Alcohols. , 2016, Organic letters.

[26]  Yehoshoa Ben‐David,et al.  Template Catalysis by Metal-Ligand Cooperation. C-C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex. , 2016, Journal of the American Chemical Society.

[27]  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.

[28]  N. Lugan,et al.  Manganese organometallic compounds in homogeneous catalysis: Past, present, and prospects , 2016 .

[29]  Guoqi Zhang,et al.  Cobalt-Catalyzed N-Alkylation of Amines with Alcohols. , 2016, Organic letters.

[30]  B. Feringa,et al.  Benzylamines via Iron-Catalyzed Direct Amination of Benzyl Alcohols , 2016 .

[31]  M. Ertl,et al.  Cobalt-Catalyzed Alkylation of Aromatic Amines by Alcohols. , 2015, Angewandte Chemie.

[32]  M. Beller,et al.  Iron-Catalyzed α-Alkylation of Ketones with Alcohols. , 2015, Angewandte Chemie.

[33]  S. Chakraborty,et al.  A Single Nickel Catalyst for the Acceptorless Dehydrogenation of Alcohols and Hydrogenation of Carbonyl Compounds , 2015 .

[34]  V. Landge,et al.  Transition-metal-catalyzed hydrogen-transfer annulations: access to heterocyclic scaffolds. , 2015, Angewandte Chemie.

[35]  Yu Zhao,et al.  Iron-catalyzed amination of alcohols assisted by Lewis acid. , 2015, Chemical communications.

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

[37]  Qin Yang,et al.  Substitution of alcohols by N-nucleophiles via transition metal-catalyzed dehydrogenation. , 2015, Chemical Society reviews.

[38]  M. Wills,et al.  C-N bond formation between alcohols and amines using an iron cyclopentadienone catalyst. , 2015, Organic letters.

[39]  B. Feringa,et al.  Iron catalysed direct alkylation of amines with alcohols , 2014, Nature Communications.

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

[41]  M. Krische,et al.  Catalytic enantioselective C-H functionalization of alcohols by redox-triggered carbonyl addition: borrowing hydrogen, returning carbon. , 2014, Angewandte Chemie.

[42]  P. Ford,et al.  Catalytic conversion of nonfood woody biomass solids to organic liquids. , 2014, Accounts of chemical research.

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

[44]  B. Scott,et al.  Understanding the mechanisms of cobalt-catalyzed hydrogenation and dehydrogenation reactions. , 2013, Journal of the American Chemical Society.

[45]  S. Pan,et al.  Recent Advances in Iridium-Catalyzed Alkylation of C–H and N–H Bonds , 2013 .

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

[47]  István T. Horváth,et al.  Valorization of Biomass: Deriving More Value from Waste , 2012, Science.

[48]  H. Neumann,et al.  The Catalytic Amination of Alcohols , 2011 .

[49]  R. Crabtree An Organometallic Future in Green and Energy Chemistry , 2011 .

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

[51]  D. M. Alonso,et al.  Catalytic conversion of biomass to biofuels , 2010 .

[52]  A. Watson,et al.  The Give and Take of Alcohol Activation , 2010, Science.

[53]  R. Crabtree,et al.  Dehydrogenation as a substrate-activating strategy in homogeneous transition-metal catalysis. , 2010, Chemical reviews.

[54]  David Milstein,et al.  Direct Synthesis of Amides from Alcohols and Amines with Liberation of H2 , 2007, Science.

[55]  Yehoshoa Ben‐David,et al.  Facile conversion of alcohols into esters and dihydrogen catalyzed by new ruthenium complexes. , 2005, Journal of the American Chemical Society.