Sulfenylation, with phenylsulfenyl chloride

Sucrose a-D-Glucopyranoside, p-D-fructofuranosyl (57-50-1), 68, 56 Sulfenylation, with phenylsulfenyl chloride, 68, 8 Sulfide, methyl p-tolyl (623-13-2), 68, 49... 

When suitably constructed unsaturated compounds, such as olefinic alcohols or unsaturated carboxylic acids 1, react with phenylsulfenyl chloride the formation of the corresponding bicyclic /j-phenylthio derivatives 3 takes place31. This presumably proceeds via the intermediacy of an episulfonium ion 2 which is captured intramolecularly by the hydroxy group leading to the final sulfenylation product 3 in high yield. 

However, the thermal stability of the adducts depends on the nature of the sulfenyl chloride and on the structure of the alkenyl group. For instance, 1-chlorosilatrane (38) and alkenyl phenyl sulfides are formed by treatment of 20 or 76 with phenylsulfenyl chloride (equation 122). It is likely that the initial adducts (86 and 87), which are unstable at — 10°C, undergo elimination reaction via the formation of an episulfonium intermediate (88), followed by nucleophilic attack of Cl at silicon. In contrast, the adducts from phenylsulfenyl chloride and trialkylalkenylsilanes are thermally stable and decompose by strong bases . The larger electron-donating ability of the silatranyl group compared with the trialkylsilyl group is most probably responsible for these diffeences in stability. 

Togni. In the presence of 5 mol% of Ti[4 -bis(diphe-nyLhydroxymethyl)-2,2-dimethyldioxoIane (TADDOL)(ate)] complex 400, the catalytic sulfenylation was effected with phenylsulfenyl chloride 399 however, the use of other sulfe-nylating reagents such as phthalimde-iV-sulfenyl chloride led to a less selective product formation. " Most recently, Shi-bata et al. reported in 2009 on the synthesis of chiral a-sul-fenyl-(3-ketoesters 404 by an enantioselective electrophilic sulfenylation of a-fluoro-p-ketoesters 402 in the presence of a catalytic amount of (/ ,/ )-4,6-dibenzofiirandiyl-2,2 -bis(4-phenyloxazoline) (DBFOX)-Ph 403/Ni(ll) complex in mod-est-to-good yields and enantioselectivities. ... 

The a-(alkylthio)ketones are dehydrogenated by phenylsulfenyl chloride (54). In this case chlorine transfer between the sulfur atoms of the reactants could be the initial and crucial step. There is little evidence asserting either a biphilic course or direct displacement at S during reaction of thiols with sulfenyl chlorides and acylsulfenyl chlorides (55). Both are soft interactions. 

Various aromatic sulfenyl chlorides, e.g. phenylsulfenyl chloride , triphenylmethylsulfenyl chloride and o-nitrophenylsulfenyl chloride , react with amines to yield the corresponding sulfenyl derivatives (reaction 13). The acylation is carried out under neutral... 

Chiral Auxiliary Chemistry The introduction of a sulfur atom to alkanes through a C—H activation is currently limited to enolizable C—H bonds such as a-sulfeny-lation of carbonyl compounds. Although there are other synthetic routes to a-sulfenylated carbonyl compounds, the preparation of chiral compounds has relied on the chiral auxiliary-assisted diastereoselective thioalkylation. In 1985, Paterson et al. reported that the chiral (9-silylated imide enolates 385 of Evans oxazolidinone could be sulfenylated with high diastereoselectivities by phenylsulfenyl chloride (Scheme 46.44). ... 

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