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. 2019 Feb 8;10(1):655.
doi: 10.1038/s41467-019-08619-x.

Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers

Biswanath Dutta  1 , Ryan Clarke  1 , Sumathy Raman  2 , Timothy D Shaffer  2 , Laura Achola  1 , Partha Nandi  3 , Steven L Suib  4   5
Affiliations

Lithium promoted mesoporous manganese oxide catalyzed oxidation of allyl ethers

Biswanath Dutta et al. Nat Commun. .

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).

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1
Schematic representation of the plausible reaction mechanism in presence of PINO, MeCN, and O2. This mechanistic scheme identifies all of the reaction intermediates, shows the various surface manganese oxide species used in the catalytic reaction, and shows a detailed set of pathways that account for observed products
Fig. 2
Fig. 2
This figure compares earlier mechanisms for acrylate formation using mixed metal oxides, oxygen, and ammonia versus this work using N-hydroxyphthalimide (NHPI), oxygen, and lithium manganese oxides which leads to enhanced (99%) selectivity for all substrates–
See this image and copyright information in PMC

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