Three sulfur atom insertion into the SS bond—pentasulfide preparation

Hou, Yihua; Abu‐Yousef, Imad A.; Harpp, David N.

doi:10.1016/s0040-4039(00)01357-5

Cited by 19 publications

(11 citation statements)

References 10 publications

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“…The chemical shifts of CH 3 S x CH 3 (xs1-5) are well documented (Table 1) (Mott and Barany 1984;Hou et al 2000). Figure 1 shows the 1 H NMR spectra of various pure dimethyl polysulfide species acquired on a 300-MHz spectrometer, possessing 1-5 sulfur atoms.…”

Section: Resultsmentioning

confidence: 72%

Quantitative 1H NMR analysis of alkaline polysulfide solutions

et al. 2005

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A novel analytical protocol for the absolute determination of the various polysulfide species present in alkaline aqueous media was developed. The method is comprised of alkylating polysulfide ions with dimethyl sulfate, followed by quantitative proton NMR spectroscopy using 1,3,5-tributyl benzene as the internal standard. In order to arrive at a quantitative acquisition protocol, a number of variables were examined in detail for their effect on the alkylation reaction, including the presence of oxygen, the amount of dimethyl sulfate and sodium hydroxide, and the various modes of adding the alkylating reagent to the reaction mixture. Most of these variables were found to play a role in determining the quantitative reliability of the procedure. Consequently, a method is described that can be used for the efficient and reliable quantitative detection of polysulfide ions. The protocol developed could be particularly useful in promoting our understanding of the intricate and delicate chemistry of polysulfide equilibria in aqueous alkaline media.

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Section: Resultsmentioning

confidence: 72%

Quantitative 1H NMR analysis of alkaline polysulfide solutions

et al. 2005

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“…We thus examined the one‐pot reaction involving the preparation of sulfenyl chloride and the subsequent chlorothiolation of a terminal alkyne (entry 20). Dimethyl disulfide was treated with sulfuryl chloride in situ to form methanesulfenyl chloride ( 2 h ) 15. Phenylacetylene ( 1 a ) and a catalytic amount of FeCl 2 were subsequently added to the reaction mixture, and the desired adduct ( E )‐ 4 t was obtained in 54 % yield with high regio‐ and stereoselectivity.…”

Section: Methodsmentioning

confidence: 99%

Iron‐Induced Regio‐ and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

et al. 2014

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The radical addition of the Cl À S s-bond in sulfenyl chlorides to various C À C triple bonds has been achieved with excellent regio-and stereoselectivity in the presence of a catalytic amount of a common iron salt. The reaction is compatible with a variety of functional groups and can be scaled up to the gram-scale with no loss in yield. As well as terminal alkynes, internal alkynes underwent stereodefined chlorothiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via iron-mediated homolysis of the ClÀS bond. The resulting chlorothiolation adducts can be readily transformed to the structurally complex alkenyl sulfides by cross-coupling reactions. The present reaction can also be applied to the complementary synthesis of the potentially useful bis-sulfoxide ligands for transition-metal-catalyzed reactions. Scheme 1. Chlorothiolation of alkynes.

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“…The precise configuration was unambiguously confirmed by single-crystal X-ray analysis of 7 ( Figure 1). [14] Next, we carried out the iron-induced chlorothiolation of various terminal alkynes 1 with benzenesulfenyl chloride (2 a) to obtain the corresponding adducts (E)-4. Instead of 1 a, various arylethynes 1 b-1 e which have an electron-donating methyl group and electron-withdrawing chloro, cyano, or trifluoromethyl groups reacted with 2 a to give the corresponding adducts (E)-4 b-4 e in good yield (Table 1,…”

mentioning

confidence: 99%

“…Dimethyl disulfide was treated with sulfuryl chloride in situ to form methanesulfenyl chloride (2 h). [15] Phenylacetylene (1 a) and a catalytic amount of FeCl 2 were subsequently added to the reaction mixture, and the desired adduct (E)-4 t was obtained in 54 % yield with high regio-and stereoselectivity.…”

mentioning

confidence: 99%

Iron‐Induced Regio‐ and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

et al. 2014

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The radical addition of the Cl-S σ-bond in sulfenyl chlorides to various C-C triple bonds has been achieved with excellent regio- and stereoselectivity in the presence of a catalytic amount of a common iron salt. The reaction is compatible with a variety of functional groups and can be scaled up to the gram-scale with no loss in yield. As well as terminal alkynes, internal alkynes underwent stereodefined chlorothiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via iron-mediated homolysis of the Cl-S bond. The resulting chlorothiolation adducts can be readily transformed to the structurally complex alkenyl sulfides by cross-coupling reactions. The present reaction can also be applied to the complementary synthesis of the potentially useful bis-sulfoxide ligands for transition-metal-catalyzed reactions.

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Three sulfur atom insertion into the SS bond—pentasulfide preparation

Cited by 19 publications

References 10 publications

Quantitative 1H NMR analysis of alkaline polysulfide solutions

Quantitative 1H NMR analysis of alkaline polysulfide solutions

Iron‐Induced Regio‐ and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

Iron‐Induced Regio‐ and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

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