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.
<p>The deoxydehydration of carbohydrates represents a key target to leverage
renewable biomass resources chemically. Using a vanadium(V)-based catalyst, we demonstrate
that it is possible to directly deoxydehydrate <i>trans</i>-cyclic diol substrates. Accompanying mechanistic
characterisation of this process by density functional calculations points to an
energetically tractable route for deoxydehydration of cyclic <i>trans</i>-diol substrates involving stepwise
cleavage of the diol C-O bonds <i>via</i>
the triplet state; experimentally, this is supported by light dependence of the
reaction. Calculations also indicate that cyclic <i>cis</i>-diols and a linear diol substrate can additionally proceed by a
concerted singlet DODH mechanism. This work potentially opens a new and
cost-effective way to efficiently convert carbohydrates of <i>trans</i>-diol stereochemistry into alkenes. </p>
<p>The deoxydehydration of carbohydrates represents a key target to leverage
renewable biomass resources chemically. Using a vanadium(V)-based catalyst, we demonstrate
that it is possible to directly deoxydehydrate <i>trans</i>-cyclic diol substrates. Accompanying mechanistic
characterisation of this process by density functional calculations points to an
energetically tractable route for deoxydehydration of cyclic <i>trans</i>-diol substrates involving stepwise
cleavage of the diol C-O bonds <i>via</i>
the triplet state; experimentally, this is supported by light dependence of the
reaction. Calculations also indicate that cyclic <i>cis</i>-diols and a linear diol substrate can additionally proceed by a
concerted singlet DODH mechanism. This work potentially opens a new and
cost-effective way to efficiently convert carbohydrates of <i>trans</i>-diol stereochemistry into alkenes. </p>
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