Change search
ReferencesLink to record
Permanent link

Direct link
Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of alpha-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Show others and affiliations
2013 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 19, no 52, 17939-17950 p.Article in journal (Refereed) Published
Abstract [en]

Gold(I)-chloride-catalyzed synthesis of -sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated -sulfenylated aldehydes and ketones in 60-97% yield. Secondary aliphatic propargylic alcohols generated -sulfenylated ketones in yields of 47-71%. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. 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. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3-position, and that the hydride from the alcohol was transferred to the 2-position of the product. 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. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2-hydride shift, generating the final product of the reaction.

Place, publisher, year, edition, pages
2013. Vol. 19, no 52, 17939-17950 p.
Keyword [en]
gold, homogeneous catalysis, reaction mechanisms, sulfenylation, synthetic methods
National Category
Chemical Sciences
URN: urn:nbn:se:su:diva-99877DOI: 10.1002/chem.201302485ISI: 000328531000036OAI: diva2:690586
Swedish Research CouncilKnut and Alice Wallenberg Foundation


Available from: 2014-01-24 Created: 2014-01-20 Last updated: 2014-01-24Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Kalek, MarcinHimo, Fahmi
By organisation
Department of Organic Chemistry
In the same journal
Chemistry - A European Journal
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 25 hits
ReferencesLink to record
Permanent link

Direct link