β-Sulfinyl acrylate esters as a convenient source of alkane- and arenesulfenate anions

Cesium (Z)‐2‐Carbomethoxyethenethiolate: A Reagent for the Preparation of (Z)‐2‐Carbomethoxyethenyl Thioethers Including Selected Cysteine and Homocysteine Derivatives

“…The Z stereochemistry of 6 is maintained at low temperature, and the reagent exhibits sulfur nucleophilicity exclusively with a variety of electrophiles. The compounds prepared have value in the preparation of sulfenate anions15 and in some cases sulfinyl chlorides 14…”

“…We have been interested in this reaction for eventual access to selected vinylic sulfoxides, which in turn are converted into α,β‐unsaturated sulfinyl chlorides 14. Also, the addition of thiols to methyl propiolate gives thioethers, which after oxidation serve as a general source of alkane‐ and arenesulfenic acid anions 15. For the latter reason we had an opportunity to react protected cysteine derivatives with methyl propiolate.…”

Bis(2-bromobenzyl) trisulfide

“…For related literature, see: Haoyun et al (2006); De Sousa et al (1990); Johnson et al (1997); Rys et al (2008). For a related synthesis see: Banerji & Kalena (1980);O'Donnell & Schwan (2003). For a related crystal structure, see: Abu-Yousef et al (2006).…”

Nucleophilic attack of 2-sulfinyl acrylates: A mild and general approach to sulfenic acid anions

“…11,13, 15 Modern developments in the generation of sulfenates involve a sulfur oxidation protocol, 5,6,16 a retro-Michael reaction, 7 fluorideinduced desilylative fragmentation chemistry 10 and an addition elimination reaction of b-sulfinyl acrylates. 8 In that latter work, we introduced the first general protocol for the release of aryland alkyl-substituted sulfenates. In this paper, we outline our full study, offering additional examples, some mechanistic implications and the introduction of n-BuLi as a sulfenate-releasing reagent.…”