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Title: Electroactivated alkylation of amines with alcohols via both direct and indirect borrowing hydrogen mechanisms

Journal Article · · Green Chemistry
DOI: https://doi.org/10.1039/c9gc03747k · OSTI ID:1801018
ORCiD logo [1];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry; OSTI
  2. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
+ Show Author Affiliations

A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called “borrowing hydrogen methodology”. Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C–H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25–70 °C and ambient pressure.

Research Organization:
National Corn Growers Association, Chesterfield, MO (United States)
Sponsoring Organization:
USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
Grant/Contract Number:
FG36-04GO14216
OSTI ID:
1801018
Journal Information:
Green Chemistry, Journal Name: Green Chemistry Journal Issue: 3 Vol. 22; ISSN 1463-9262
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Biaryl Phosphane Ligands in Palladium-Catalyzed Amination journal August 2008
Spezifische Protonenacceptoren als Hilfsbasen bei Alkylierungs- und Dehydrohalogenierungsreaktionen journal February 1958
The “Borrowing Hydrogen Strategy” by Supported Ruthenium Hydroxide Catalysts: Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines journal May 2010
Utilization of Common Ligands for the Ruthenium-Catalyzed Amination of Alcohols journal November 2013
Mechanistic Aspects of C—H Activation by Pt Complexes journal September 2005
Stereoretentive H/D Exchange via an Electroactivated Heterogeneous Catalyst at sp 3 C-H Sites Bearing Amines or Alcohols : Stereoretentive H/D Exchange via an Electroactivated Heterogeneous Catalyst at sp journal July 2016
Dissociationsvorgänge bei den einatomigen Alkoholen, Aethern und Salzen journal January 1901
Heterogeneously catalyzed selective N-alkylation of aromatic and heteroaromatic amines with alcohols by a supported ruthenium hydroxide journal April 2009
N-alkylation of amines with alcohols over alumina-entrapped Ag catalysts using the “borrowing hydrogen” methodology journal August 2012
N-Methylation of amines and nitroarenes with methanol using heterogeneous platinum catalysts journal March 2019
Palladium catalyzed N-alkylation of amines with alcohols journal March 2011
Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis journal January 2018
Ruthenium-Catalyzed Amination of Secondary Alcohols Using Borrowing Hydrogen Methodology journal February 2016
Mechanistic Aspects of C−H Activation by Pt Complexes journal June 2005
Heterogeneous Catalysts for the Guerbet Coupling of Alcohols journal June 2013
Electrocatalysis on Oxide-Stabilized, High-Surface Area Carbon Electrodes journal July 2013
Estimation of Absolute Free Energies of Hydration Using Continuum Methods:  Accuracy of Partial Charge Models and Optimization of Nonpolar Contributions journal November 2005
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Catalytic Alkylation of Aniline journal August 1924
Multialkylation of Aqueous Ammonia with Alcohols Catalyzed by Water-Soluble Cp*Ir−Ammine Complexes journal November 2010
Complementation of Biotransformations with Chemical C–H Oxidation: Copper-Catalyzed Oxidation of Tertiary Amines in Complex Pharmaceuticals journal August 2013
Ruthenium-Catalyzed N -Alkylation of Amines and Sulfonamides Using Borrowing Hydrogen Methodology journal February 2009
Stereoselective reductions of substituted cyclohexyl and cyclopentyl carbon-nitrogen .pi. systems with hydride reagents journal October 1983
Borrowing Hydrogen Methodology for Amine Synthesis under Solvent-Free Microwave Conditions journal April 2011
Ruthenium Complex-Controlled Catalytic N -Mono- or N,N -Dialkylation of Heteroaromatic Amines with Alcohols journal January 1996
Gauge-Including Atomic Orbital Proton Chemical Shifts of Strong Hydrogen Bonds:  The Importance of Electron Correlation journal May 2001
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Model for Aqueous Solvation Based on Class IV Atomic Charges and First Solvation Shell Effects journal January 1996
Stereoretentive C−H Bond Activation in the Aqueous Phase Catalytic Hydrogenation of Amino Acids to Amino Alcohols journal February 2003
Selective Synthesis of Secondary and Tertiary Amines by Cp*Iridium-Catalyzed Multialkylation of Ammonium Salts with Alcohols journal January 2008
Ultrastructural Characterization of the Lower Motor System in a Mouse Model of Krabbe Disease journal December 2016
Heterogeneous catalysis for the direct synthesis of chemicals by borrowing hydrogen methodology journal January 2015
Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals journal January 2019
Mild electrocatalytic hydrogenation and hydrodeoxygenation of bio-oil derived phenolic compounds using ruthenium supported on activated carbon cloth journal January 2012
Transition metal-catalysed N-alkylation of amines by alcohols journal January 1981
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
IUPAC-NIST Solubility Data Series. 82. Alcohols with Water—Revised and Updated: Part 1. C4 Alcohols with Water journal March 2007
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
A comparison of models for calculating nuclear magnetic resonance shielding tensors journal April 1996
Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models journal January 1998
Selective Synthesis of Secondary Amines via N -Alkylation of Primary Amines and Ammonia with Alcohols by Supported Copper Hydroxide Catalysts journal November 2010
Surfactants: Pharmaceutical and Medicinal Aspects [Surfactants: Pharmaceutical and Medicinal Aspects] journal May 2013

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