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

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Biswas, SrijitUppsala universitet,Syntetisk organisk kemi (författare)

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

Artikel/kapitelEngelska2013

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2013-11-22
Wiley,2013
printrdacarrier

Nummerbeteckningar

LIBRIS-ID:oai:DiVA.org:su-99877
https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-99877URI
https://doi.org/10.1002/chem.201302485DOI
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-215902URI

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Språk:engelska
Sammanfattning på:engelska

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Ämneskategori:art swepub-publicationtype

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AuthorCount:6;
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.

Ämnesord och genrebeteckningar

NATURVETENSKAP Kemi hsv//swe
NATURAL SCIENCES Chemical Sciences hsv//eng
gold
homogeneous catalysis
reaction mechanisms
sulfenylation
synthetic methods

Biuppslag (personer, institutioner, konferenser, titlar ...)

Dahlstrand, ChristianUppsala universitet,Fysikalisk-organisk kemi(Swepub:uu)chrda875 (författare)
Watile, Rahul A.Uppsala universitet,Syntetisk organisk kemi (författare)
Kalek, MarcinStockholms universitet,Institutionen för organisk kemi(Swepub:su)maka9675 (författare)
Himo, FahmiStockholms universitet,Institutionen för organisk kemi(Swepub:su)himo (författare)
Samec, Joseph S. M.Uppsala universitet,Syntetisk organisk kemi(Swepub:uu)jossa512 (författare)
Uppsala universitetSyntetisk organisk kemi (creator_code:org_t)

Sammanhörande titlar

Ingår i:Chemistry - A European Journal: Wiley19:52, s. 17939-179500947-65391521-3765

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Av författaren/redakt...: Biswas, Srijit; Dahlstrand, Chri ...; Watile, Rahul A.; Kalek, Marcin; Himo, Fahmi; Samec, Joseph S. ...

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NATURVETENSKAP: NATURVETENSKAP; och Kemi

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Av lärosätet: Stockholms universitet; Uppsala universitet

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