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Deoxydehydration (DODH) is an efficient process for the removal of vicinal OH groups of a diol or polyol. Conventional DODH reactions usually take place at a single-site MOx (M=Re, Mo, V etc.) active center, which proceed through a diol condensation step, an alkene extrusion step and a catalyst regeneration (or reduction) step. Here, we suggest that MoS2-supported transition metal atoms allow for the DODH reaction to occur through an alternative mechanism, whereby the C-H bond of a diol is activated first, which facilitates the C-OH bond cleavage on a neighboring carbon. The removal of the second OH group is also facile over the proposed catalysts. Our kinetic studies suggest that the DODH of ethylene glycol on Ru2/MoS2, Ir2/MoS2 and Ru3/MoS2 are highly active with predicted turnover frequencies of over 1/s. Thus, our study suggests a possible approach for the design of highly active DODH catalysts. Apart from being a DODH catalyst, the proposed MoS2-supported catalysts are also highly active as hydrodeoxygenation catalyst for the removal of alcohol OH groups.
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Chiral Diol-Based Organocatalysts in Enantioselective Reactions
Organocatalysis has emerged as a powerful synthetic tool in organic chemistry in the last few decades. Among various classes of organocatalysis, chiral diol-based scaffolds, such as BINOLs, VANOLs, and tartaric acid derivatives, have been widely used to induce enantioselectivity due to the ability of the hydroxyls to coordinate with the Lewis acidic sites of reagents or substrates and create a chiral environment for the transformation. In this review, we will discuss the applications of these diol-based catalysts in different types of reactions, including the scopes of reactions and the modes of catalyst activation. In general, the axially chiral aryl diol BINOL and VANOL derivatives serve as the most competent catalyst for most examples, but examples of exclusive success using other scaffolds, herein, suggests that they should not be overlooked. Lastly, the examples, to date, are mainly from tartrate and biaryl diol catalysts, suggesting that innovation may be available from new diol scaffolds.
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- Award ID(s):
- 1800499
- PAR ID:
- 10093681
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 23
- Issue:
- 9
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 2317
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/molecules23092317
