Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers
Abstract
Herein we report the first example of the catalytic aerobic partial oxidation of allyl ether to its acrylate ester derivative. Many partial oxidations often need an expensive oxidant such as peroxides or other species to drive such reactions. In addition, selective generation of esters using porous catalysts has been elusive. This reaction is catalyzed by a Li ion promoted mesoporous manganese oxide (meso-Mn2O3) under mild conditions with no precious metals, a reusable heterogeneous catalyst, and easy isolation. This process is very attractive for the oxidation of allyl ethers. We report on the catalytic activity, selectivity, and scope of the reaction. In the best cases presented, almost complete conversion of allyl ether with near complete chemo-selectivity towards acrylate ester derivatives is observed. Based on results from controlled experiments, we propose a possible reaction mechanism for the case in which N-hydroxyphthalimide (NHPI) is used in combination with trichloroacetonitrile (CCl3CN).
- Authors:
-
[1];
- Univ. of Connecticut, Storrs, CT (United States)
- ExxonMobil, Annandale, NJ (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, and Biosciences Division
- Contributing Org.:
- ExxonMobil Research and Engineering Company
- OSTI Identifier:
- 1598195
- Grant/Contract Number:
- FG02-86ER13622
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Dutta, Biswanath, Clarke, Ryan, Raman, Sumathy, Shaffer, Timothy D., Achola, Laura, Nandi, Partha, and Suib, Steven L. Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers. United States: N. p., 2019.
Web. doi:10.1038/s41467-019-08619-x.
Dutta, Biswanath, Clarke, Ryan, Raman, Sumathy, Shaffer, Timothy D., Achola, Laura, Nandi, Partha, & Suib, Steven L. Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers. United States. https://doi.org/10.1038/s41467-019-08619-x
Dutta, Biswanath, Clarke, Ryan, Raman, Sumathy, Shaffer, Timothy D., Achola, Laura, Nandi, Partha, and Suib, Steven L. Fri .
"Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers". United States. https://doi.org/10.1038/s41467-019-08619-x. https://www.osti.gov/servlets/purl/1598195.
@article{osti_1598195,
title = {Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers},
author = {Dutta, Biswanath and Clarke, Ryan and Raman, Sumathy and Shaffer, Timothy D. and Achola, Laura and Nandi, Partha and Suib, Steven L.},
abstractNote = {Herein we report the first example of the catalytic aerobic partial oxidation of allyl ether to its acrylate ester derivative. Many partial oxidations often need an expensive oxidant such as peroxides or other species to drive such reactions. In addition, selective generation of esters using porous catalysts has been elusive. This reaction is catalyzed by a Li ion promoted mesoporous manganese oxide (meso-Mn2O3) under mild conditions with no precious metals, a reusable heterogeneous catalyst, and easy isolation. This process is very attractive for the oxidation of allyl ethers. We report on the catalytic activity, selectivity, and scope of the reaction. In the best cases presented, almost complete conversion of allyl ether with near complete chemo-selectivity towards acrylate ester derivatives is observed. Based on results from controlled experiments, we propose a possible reaction mechanism for the case in which N-hydroxyphthalimide (NHPI) is used in combination with trichloroacetonitrile (CCl3CN).},
doi = {10.1038/s41467-019-08619-x},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {Fri Feb 08 00:00:00 EST 2019},
month = {Fri Feb 08 00:00:00 EST 2019}
}
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Ion induced promotion of activity enhancement of mesoporous manganese oxides for aerobic oxidation reactions
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Efficient dehydration of methyl lactate to acrylic acid using Ca3(PO4)2–SiO2 catalyst
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Interpretation of vibrational and NMR spectra of allyl acrylate: An evidence for several conformers
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Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials
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Efficient Acrylic Acid Production through Bio Lactic Acid Dehydration over NaY Zeolite Modified by Alkali Phosphates
journal, December 2010
- Zhang, Junfeng; Zhao, Yuling; Pan, Min
- ACS Catalysis, Vol. 1, Issue 1
Multifunctionality of Crystalline MoV(TeNb) M1 Oxide Catalysts in Selective Oxidation of Propane and Benzyl Alcohol
journal, April 2013
- Amakawa, Kazuhiko; Kolen’ko, Yury V.; Villa, Alberto
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Catalytic Decomposition of Hydrogen Peroxide on Iron Oxide: Kinetics, Mechanism, and Implications
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A Study about the Propane Ammoxidation to Acrylonitrile with an Alumina-Supported Sb−V−O Catalyst
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Catalytic Dehydrogenation of Propane in Hydrogen Permselective Membrane Reactors
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Roles of Surface Te, Nb, and Sb Oxides in Propane Oxidation to Acrylic Acid over Bulk Orthorhombic Mo−V−O Phase
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- Guliants, Vadim V.; Bhandari, Rishabh; Swaminathan, Balasubramanian
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CCl 3 CN: A Crucial Promoter of m CPBA-Mediated Direct Ether Oxidation
journal, September 2010
- Kamijo, Shin; Matsumura, Shoko; Inoue, Masayuki
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Scalable and sustainable electrochemical allylic C–H oxidation
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- Horn, Evan J.; Rosen, Brandon R.; Chen, Yong
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A general approach to crystalline and monomodal pore size mesoporous materials
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- Poyraz, Altug S.; Kuo, Chung-Hao; Biswas, Sourav
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Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides
journal, September 2018
- Biswas, Sourav; Khanna, Harshul S.; Nizami, Quddus A.
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Synthesis and Rheological Studies of Methacrylic Acid‐Ethyl Acrylate–Allyl Methacrylate Terpolymers
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