Gold(I)-catalysed direct thioetherifications using allylic alcohols: An experimental and computational study

Lorena Herkert; Samantha L.J. Green; Graeme Barker; David G. Johnson; Paul C. Young; Stuart A. Macgregor; Ai Lan Lee

doi:10.1002/chem.201403293

Gold(I)-catalysed direct thioetherifications using allylic alcohols: An experimental and computational study

Lorena Herkert, Samantha L.J. Green, Graeme Barker, David G. Johnson, Paul C. Young, Stuart A. Macgregor^*, Ai Lan Lee

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

Abstract

A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (S_N2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products. Gold case: A regioselective gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate (see scheme). The mechanism and origins of the observed selectivities are elucidated by a computational study.

Original language	English
Pages (from-to)	11540-11548
Number of pages	9
Journal	Chemistry - A European Journal
Volume	20
Issue number	36
DOIs	https://doi.org/10.1002/chem.201403293
Publication status	Published - 1 Sept 2014

Keywords

allylation
allylic alcohols
gold
mechanism
thiols

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title = "Gold(I)-catalysed direct thioetherifications using allylic alcohols: An experimental and computational study",

abstract = "A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products. Gold case: A regioselective gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate (see scheme). The mechanism and origins of the observed selectivities are elucidated by a computational study.",

keywords = "allylation, allylic alcohols, gold, mechanism, thiols",

author = "Lorena Herkert and Green, {Samantha L.J.} and Graeme Barker and Johnson, {David G.} and Young, {Paul C.} and Macgregor, {Stuart A.} and Lee, {Ai Lan}",

year = "2014",

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doi = "10.1002/chem.201403293",

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AU - Herkert, Lorena

AU - Green, Samantha L.J.

AU - Barker, Graeme

AU - Johnson, David G.

AU - Young, Paul C.

AU - Macgregor, Stuart A.

AU - Lee, Ai Lan

PY - 2014/9/1

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N2 - A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products. Gold case: A regioselective gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate (see scheme). The mechanism and origins of the observed selectivities are elucidated by a computational study.

AB - A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products. Gold case: A regioselective gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate (see scheme). The mechanism and origins of the observed selectivities are elucidated by a computational study.

KW - allylation

KW - allylic alcohols

KW - gold

KW - mechanism

KW - thiols

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JO - Chemistry - A European Journal

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ER -

Gold(I)-catalysed direct thioetherifications using allylic alcohols: An experimental and computational study

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Keywords

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