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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Fältnamn	Indikatorer	Metadata
000		04102naa a2200481 4500
001		oai:DiVA.org:su-99877
003		SwePub
008		140120s2013 \| \|\|\|\|\|\|\|\|\|\|\|000 \|\|eng\|
009		oai:DiVA.org:uu-215902
024	7	a https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-998772 URI
024	7	a https://doi.org/10.1002/chem.2013024852 DOI
024	7	a https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-2159022 URI
040		a (SwePub)sud (SwePub)uu
041		a engb eng
042		9 SwePub
072	7	a ref2 swepub-contenttype
072	7	a art2 swepub-publicationtype
100	1	a Biswas, Srijitu Uppsala universitet,Syntetisk organisk kemi4 aut0 (Swepub:uu)sribi464
245	1 0	a Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of alpha-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols :b Substrate Scope and Experimental and Theoretical Mechanistic Investigation
264		c 2013-11-22
264	1	b Wiley,c 2013
338		a print2 rdacarrier
500		a AuthorCount:6;
520		a 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.
650	7	a NATURVETENSKAPx Kemi0 (SwePub)1042 hsv//swe
650	7	a NATURAL SCIENCESx Chemical Sciences0 (SwePub)1042 hsv//eng
653		a gold
653		a homogeneous catalysis
653		a reaction mechanisms
653		a sulfenylation
653		a synthetic methods
700	1	a Dahlstrand, Christianu Uppsala universitet,Fysikalisk-organisk kemi4 aut0 (Swepub:uu)chrda875
700	1	a Watile, Rahul A.u Uppsala universitet,Syntetisk organisk kemi4 aut
700	1	a Kalek, Marcinu Stockholms universitet,Institutionen för organisk kemi4 aut0 (Swepub:su)maka9675
700	1	a Himo, Fahmiu Stockholms universitet,Institutionen för organisk kemi4 aut0 (Swepub:su)himo
700	1	a Samec, Joseph S. M.u Uppsala universitet,Syntetisk organisk kemi4 aut0 (Swepub:uu)jossa512
710	2	a Uppsala universitetb Syntetisk organisk kemi4 org
773	0	t Chemistry - A European Journald : Wileyg 19:52, s. 17939-17950q 19:52<17939-17950x 0947-6539x 1521-3765
856	4	u https://doi.org/10.1002/chem.201302485y Fulltext
856	4	u https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/chem.201302485
856	4 8	u https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-99877
856	4 8	u https://doi.org/10.1002/chem.201302485
856	4 8	u https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-215902

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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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