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Direct Deoxydehydration of Cyclic trans ‐Diol Substrates: An Experimental and Computational Study of the Reaction Mechanism of Vanadium(V)‐based Catalysis **
Author(s) -
Aksanoglu Ebru,
Lim Yee Hwee,
Bryce Richard A.
Publication year - 2021
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.202002594
Subject(s) - diol , vanadium , catalysis , chemistry , singlet state , reaction mechanism , density functional theory , computational chemistry , enantioselective synthesis , combinatorial chemistry , organic chemistry , physics , nuclear physics , excited state
The deoxydehydration of carbohydrates represents a key target to leverage renewable biomass resources chemically. Using a vanadium(V)‐based catalyst, it was possible to directly deoxydehydrate cyclic trans ‐diol substrates. Accompanying mechanistic characterisation of this process by density functional calculations pointed to an energetically tractable route for deoxydehydration of cyclic trans ‐diol substrates involving stepwise cleavage of the diol C−O bonds via the triplet state; experimentally, this was supported by light dependence of the reaction. Calculations also indicated that cyclic cis ‐diols and a linear diol substrate could additionally proceed by a concerted singlet DODH mechanism. This work potentially opens a new and cost‐effective way to efficiently convert carbohydrates of trans ‐diol stereochemistry into alkenes.