Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol

Karakalos, Stavros; Zugic, Branko; Stowers, Kara J.; Biener, Monika M.; Biener, Juergen; Friend, Cynthia M.; Madix, Robert J.

doi:10.1016/j.susc.2016.03.017

Title: Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol

Journal Article · Fri Mar 18 00:00:00 EDT 2016 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2016.03.017· OSTI ID:1416497

^[1]; Zugic, Branko ^[1]; Stowers, Kara J. ^[1]; Biener, Monika M. ^[2]; Biener, Juergen ^[2]; Friend, Cynthia M. ^[3]; Madix, Robert J. ^[4]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, School of Engineering and Applied Sciences
Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences

Modern methods of esterification, one of the most important reactions in organic synthesis, are reaching their limits, as far as waste and expense are concerned. Novel chemical approaches to ester formation are therefore of importance. We report a simple procedure free of caustic reagents or byproducts for the facile direct oxidative methyl esterification of aldehydes over nanoporous Au catalysts. Complementary model studies on single crystal gold surfaces establish the fundamental reactions involved. We also find that methanol more readily reacts with adsorbed active oxygen than do the aldehydes, but that once the aldehydes do react, they form strongly-bound acrylates that block reactive sites and decrease the yields of acrylic esters under steady flow conditions at 420 K. We can achieve significant improvements in yield by operating at higher temperatures, which render the site-blocking acrylates unstable.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; SC0012573

OSTI ID:: 1416497

Alternate ID(s):: OSTI ID: 1397443

Report Number(s):: LLNL-JRNL-737636

Journal Information:: Surface Science, Vol. 652, Issue C; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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Bio‐Acrylates Production: Recent Catalytic Advances and Perspectives of the Use of Lactic Acid and Their Derivates Makshina, Ekaterina V.; Canadell, Judit; van Krieken, Jan ChemCatChem, Vol. 11, Issue 1 https://doi.org/10.1002/cctc.201801494	journal	October 2018
Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110) O'Connor, Christopher R.; Hiebel, Fanny; Chen, Wei Chemical Science, Vol. 9, Issue 15 https://doi.org/10.1039/c7sc05313d	journal	January 2018

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aldehyde esterification
oxidative cross-coupling
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Title: Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol

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