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Title: Aerobic Self-Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide

Abstract

Aerobic self-esterification of primary alcohols catalyzed by mesoporous metal oxides (manganese and cobalt oxides) is reported under base and solvent free conditions. For a range of aliphatic alcohols, up to 90 % conversions to esters was achieved. The catalytic reaction is likewise applicable to neat aldehydes as substrates with yields of up to 86 %. High pressure batch reaction for ethanol to ethyl acetate led to 22 % yield. Isotope labeling studies indicated decarboxylation on the catalyst surface. Mechanistic and kinetic experiments implicate oxygen rebound and α-carbon removal as intermediate steps. Finally, mesoporous cobalt oxide showed about 20 % higher catalytic activity compared to mesoporous manganese oxide.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Univ. of Connecticut, Storrs, CT (United States)
Publication Date:
Research Org.:
Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1598199
Alternate Identifier(s):
OSTI ID: 1544451
Grant/Contract Number:  
FG02-86ER13622
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 15; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; esterification; transition metal oxides; mesoporous materials; aerobic oxidation

Citation Formats

Moharreri, Ehsan, Biswas, Sourav, Deljoo, Bahareh, Kriz, David, Lim, Seyoung, Elliott, Sarah, Dissanayake, Shanka, Dabaghian, Marina, Aindow, Mark, and Suib, Steven L. Aerobic Self-Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide. United States: N. p., 2019. Web. doi:10.1002/cctc.201900704.
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Moharreri, Ehsan, Biswas, Sourav, Deljoo, Bahareh, Kriz, David, Lim, Seyoung, Elliott, Sarah, Dissanayake, Shanka, Dabaghian, Marina, Aindow, Mark, & Suib, Steven L. Aerobic Self-Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide. United States. https://doi.org/10.1002/cctc.201900704
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Moharreri, Ehsan, Biswas, Sourav, Deljoo, Bahareh, Kriz, David, Lim, Seyoung, Elliott, Sarah, Dissanayake, Shanka, Dabaghian, Marina, Aindow, Mark, and Suib, Steven L. Sun . "Aerobic Self-Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide". United States. https://doi.org/10.1002/cctc.201900704. https://www.osti.gov/servlets/purl/1598199.
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@article{osti_1598199,
title = {Aerobic Self-Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide},
author = {Moharreri, Ehsan and Biswas, Sourav and Deljoo, Bahareh and Kriz, David and Lim, Seyoung and Elliott, Sarah and Dissanayake, Shanka and Dabaghian, Marina and Aindow, Mark and Suib, Steven L.},
abstractNote = {Aerobic self-esterification of primary alcohols catalyzed by mesoporous metal oxides (manganese and cobalt oxides) is reported under base and solvent free conditions. For a range of aliphatic alcohols, up to 90 % conversions to esters was achieved. The catalytic reaction is likewise applicable to neat aldehydes as substrates with yields of up to 86 %. High pressure batch reaction for ethanol to ethyl acetate led to 22 % yield. Isotope labeling studies indicated decarboxylation on the catalyst surface. Mechanistic and kinetic experiments implicate oxygen rebound and α-carbon removal as intermediate steps. Finally, mesoporous cobalt oxide showed about 20 % higher catalytic activity compared to mesoporous manganese oxide.},
doi = {10.1002/cctc.201900704},
journal = {ChemCatChem},
number = 15,
volume = 11,
place = {United States},
year = {Sun Jun 09 00:00:00 EDT 2019},
month = {Sun Jun 09 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/cctc.201900704
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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Representative SE SEM images of meso MnOx-350 (a), CoOx-350(b), Cs-promoted MnOx-350 (c), and CoOx-350 (d).
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Works referenced in this record:

Transformation of alcohols to esters promoted by hydrogen bonds using oxygen as the oxidant under metal-free conditions
journal, October 2018

Direct oxidative esterification of alcohols
journal, January 2014

  • Tang, Shan; Yuan, Jiwen; Liu, Chao
  • Dalton Trans., Vol. 43, Issue 36
  • DOI: 10.1039/C4DT01133C

Controllable synthesis of mesoporous cobalt oxide for peroxide free catalytic epoxidation of alkenes under aerobic conditions
journal, February 2018

Catalytic Transformation of Aliphatic Alcohols to Corresponding Esters in O 2 under Neutral Conditions Using Visible-Light Irradiation
journal, January 2015

  • Xiao, Qi; Liu, Zhe; Bo, Arixin
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja511619c

Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes
journal, August 2005

  • Zhang, Jing; Leitus, Gregory; Ben-David, Yehoshoa
  • Journal of the American Chemical Society, Vol. 127, Issue 31
  • DOI: 10.1021/ja052862b

Palladium-Catalyzed Aerobic Oxidative Direct Esterification of Alcohols
journal, April 2011

Mesoporous Manganese Oxide Catalyzed Aerobic Oxidative Coupling of Anilines To Aromatic Azo Compounds
journal, January 2016

  • Dutta, Biswanath; Biswas, Sourav; Sharma, Vinit
  • Angewandte Chemie International Edition, Vol. 55, Issue 6
  • DOI: 10.1002/anie.201508223

Highly efficient self-esterification of aliphatic alcohols using supported gold nanoparticles under mild conditions
journal, November 2016

Mechanistic Studies of the Oxidative Dehydrogenation of Methanol Using a Cationic Palladium Complex
journal, July 2009

  • Pearson, David M.; Waymouth, Robert M.
  • Organometallics, Vol. 28, Issue 13
  • DOI: 10.1021/om900217s

A general approach to crystalline and monomodal pore size mesoporous materials
journal, December 2013

  • Poyraz, Altug S.; Kuo, Chung-Hao; Biswas, Sourav
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3952

Palladium-Catalyzed Carbonylation Reactions of Aryl Halides and Related Compounds
journal, May 2009

  • Brennführer, Anne; Neumann, Helfried; Beller, Matthias
  • Angewandte Chemie International Edition, Vol. 48, Issue 23
  • DOI: 10.1002/anie.200900013

Crystalline Mesoporous K 2– x Mn 8 O 16 and ε-MnO 2 by Mild Transformations of Amorphous Mesoporous Manganese Oxides and Their Enhanced Redox Properties
journal, June 2014

  • Poyraz, Altug S.; Song, Wenqiao; Kriz, David
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 14
  • DOI: 10.1021/am502846e

Oxidant controlled Pd-catalysed selective oxidation of primary alcohols
journal, January 2013

  • Liu, Chao; Tang, Shan; Lei, Aiwen
  • Chemical Communications, Vol. 49, Issue 13
  • DOI: 10.1039/c2cc38086b

Mesoporous Co 3 O 4 with Controlled Porosity: Inverse Micelle Synthesis and High-Performance Catalytic CO Oxidation at −60 °C
journal, July 2014

  • Song, Wenqiao; Poyraz, Altug S.; Meng, Yongtao
  • Chemistry of Materials, Vol. 26, Issue 15
  • DOI: 10.1021/cm502106v

Base-Free Oxidation of Alcohols to Esters at Room Temperature and Atmospheric Conditions using Nanoscale Co-Based Catalysts
journal, February 2015

  • Zhong, Wei; Liu, Hongli; Bai, Cuihua
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs502101c

Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations
journal, July 2001

  • Corma, Avelino; Nemeth, Laszlo T.; Renz, Michael
  • Nature, Vol. 412, Issue 6845
  • DOI: 10.1038/35086546

Ruthenium-catalyzed oxidative transformation of alcohols and aldehydes to esters and lactones
journal, September 1987

  • Murahashi, Shunichi; Naota, Takeshi; Ito, Keiichiro
  • The Journal of Organic Chemistry, Vol. 52, Issue 19
  • DOI: 10.1021/jo00228a032

General and Selective Palladium-Catalyzed Oxidative Esterification of Alcohols
journal, April 2011

  • Gowrisankar, Saravanan; Neumann, Helfried; Beller, Matthias
  • Angewandte Chemie International Edition, Vol. 50, Issue 22
  • DOI: 10.1002/anie.201008035

Selective Oxidation of Alcohols to Esters Using Heterogeneous Co 3 O 4 –N@C Catalysts under Mild Conditions
journal, July 2013

  • Jagadeesh, Rajenahally V.; Junge, Henrik; Pohl, Marga-Martina
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403615c

Ion induced promotion of activity enhancement of mesoporous manganese oxides for aerobic oxidation reactions
journal, April 2015

Esterification and Transesterification of Renewable Chemicals
journal, February 2004

Efficient and Simple Approaches Towards Direct Oxidative Esterification of Alcohols
journal, October 2014

  • Ray, Ritwika; Jana, Rahul Dev; Bhadra, Mayukh
  • Chemistry - A European Journal, Vol. 20, Issue 47
  • DOI: 10.1002/chem.201403786

Copper-Catalyzed Cross-Coupling of Thiols, Alcohols, and Oxygen for the Synthesis of Esters: Copper-Catalyzed Cross-Coupling for the Synthesis of Esters
journal, December 2014

  • Lim, Seungyeon; Ji, Miran; Wang, Xi
  • European Journal of Organic Chemistry, Vol. 2015, Issue 3
  • DOI: 10.1002/ejoc.201403311

Mesoporous cobalt/manganese oxide: a highly selective bifunctional catalyst for amine–imine transformations
journal, January 2018

  • Dutta, Biswanath; March, Seth; Achola, Laura
  • Green Chemistry, Vol. 20, Issue 14
  • DOI: 10.1039/C8GC00862K

Studies of the Hierarchical Structure in UCT Manganese Oxides
journal, July 2017

  • Deljoo, Bahareh; Jafari, Tahereh; Suib, Steven L.
  • Microscopy and Microanalysis, Vol. 23, Issue S1
  • DOI: 10.1017/S1431927617009989

Comprehensive Magnetic Study of Nanostructured Mesoporous Manganese Oxide Materials and Implications for Catalytic Behavior
journal, January 2018

High-Performance Catalytic CH 4 Oxidation at Low Temperatures: Inverse Micelle Synthesis of Amorphous Mesoporous Manganese Oxides and Mild Transformation to K 2– x Mn 8 O 16 and ϵ-MnO 2
journal, January 2015

  • Wasalathanthri, Niluka D.; Poyraz, Altug S.; Biswas, Sourav
  • The Journal of Physical Chemistry C, Vol. 119, Issue 3
  • DOI: 10.1021/jp5108558

General and Selective Palladium-Catalyzed Oxidative Esterification of Alcohols
journal, April 2011

  • Gowrisankar, Saravanan; Neumann, Helfried; Beller, Matthias
  • Angewandte Chemie, Vol. 123, Issue 22
  • DOI: 10.1002/ange.201008035

Mesoporous Manganese Oxide Catalyzed Aerobic Oxidative Coupling of Anilines To Aromatic Azo Compounds
journal, January 2016

  • Dutta, Biswanath; Biswas, Sourav; Sharma, Vinit
  • Angewandte Chemie, Vol. 128, Issue 6
  • DOI: 10.1002/ange.201508223

Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes.
journal, December 2005

Palladium-Catalyzed Aerobic Oxidative Direct Esterification of Alcohols
journal, April 2011

  • Liu, Chao; Wang, Jing; Meng, Lingkui
  • Angewandte Chemie International Edition, Vol. 50, Issue 22
  • DOI: 10.1002/anie.201008073
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    Figures / Tables found in this record:

    Figure 1 (p. 8)figure
    Table 1 (p. 8)table
    Scheme 1 (p. 9)figure
    Table 2 (p. 9)table
    Table 3 (p. 10)table
    Table 4 (p. 11)table
    Table 5 (p. 12)table
    Table 6: Part 1 (p. 13)table
    Table 6: Part 2 (p. 14)table
    Table 7 (p. 15)table
    Scheme 2 (p. 16)figure
    Table 8 (p. 17)table
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