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Atom-efficient gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols: substrate scope and experimental and theoretical mechanistic investigation.

Biswas S, Dahlstrand C, Watile RA, Kalek M, Himo F, Samec JS - Chemistry (2013)

Bottom Line: A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction.Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2-position of propargylic alcohol was determined by a low-energy, five-membered cyclic protodeauration transition state instead of the strained, four-membered cyclic transition state found for attack at the 3-position.This in turn allows for a 1,2-hydride shift, generating the final product of the reaction.

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Affiliation: Department of Chemistry, BMC, Uppsala University, Box 576, 75123, Uppsala (Sweden), Fax: (+46) 018-471-3818.

No MeSH data available.


Traditional synthesis of α-sulfenylated carbonyl compounds.
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sch02: Traditional synthesis of α-sulfenylated carbonyl compounds.


Atom-efficient gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols: substrate scope and experimental and theoretical mechanistic investigation.

Biswas S, Dahlstrand C, Watile RA, Kalek M, Himo F, Samec JS - Chemistry (2013)

Traditional synthesis of α-sulfenylated carbonyl compounds.
© Copyright Policy
Related In: Results  -  Collection

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getmorefigures.php?uid=PMC4524420&req=5

sch02: Traditional synthesis of α-sulfenylated carbonyl compounds.
Bottom Line: A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction.Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2-position of propargylic alcohol was determined by a low-energy, five-membered cyclic protodeauration transition state instead of the strained, four-membered cyclic transition state found for attack at the 3-position.This in turn allows for a 1,2-hydride shift, generating the final product of the reaction.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, BMC, Uppsala University, Box 576, 75123, Uppsala (Sweden), Fax: (+46) 018-471-3818.

No MeSH data available.