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Dual-Function of Alcohols in Gold-Mediated Selective Coupling of Amines and Alcohols

  1. Dr. Bingjun Xu1,
  2. Prof. Robert J. Madix2,
  3. Prof. Cynthia M. Friend1,2,*

Article first published online: 17 JAN 2012

DOI: 10.1002/chem.201103232

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 18, Issue 8, pages 2313–2318, February 20, 2012

Additional Information

How to Cite

Xu, B., Madix, R. J. and Friend, C. M. (2012), Dual-Function of Alcohols in Gold-Mediated Selective Coupling of Amines and Alcohols. Chem. Eur. J., 18: 2313–2318. doi: 10.1002/chem.201103232

Author Information

  1. 1

    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138 (USA), Fax: (+1) 617-496-8410

  2. 2

    School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138 (USA)

*Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138 (USA), Fax: (+1) 617-496-8410

Publication History

  1. Issue published online: 10 FEB 2012
  2. Article first published online: 17 JAN 2012
  3. Manuscript Received: 12 OCT 2011

Funded by

  • Department of Energy. Grant Number: FG02–84-ER13289
  • National Science Foundation. Grant Number: CHE-0952790
  • Harvard University Center for the Environment

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Keywords:

  • coupling;
  • dual-function;
  • excess atomic oxygen;
  • gold;
  • selectivity

Abstract

Oxidative coupling of alcohols (methanol and ethanol) and dimethylamine on atomic-oxygen-activated Au(111) occurs entirely on the surface to form the corresponding amides when the alkoxy of the alcohol and the amide derived from the amine are co-adsorbed. For effective oxygen-assisted coupling the formation of the amide requires excess methanol. Mechanistic studies reveal that molecularly adsorbed methanol removes excess adsorbed atomic oxygen efficiently, precluding either secondary oxidation or oxidative dehydrogenation of dimethylamide to the imine. The adsorbed amide then can react with the aldehyde produced by β-hydride elimination from the alkoxy to form the hemiaminal, the reactive intermediate leading to coupling. The selectivity for formamide production can be increased to nearly 100 % in excess methanol.

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