Chemistry of sulphenyl halides and sulphenamides

2,3‐Disubstituted Benzo[b]thiophenes from Diarylalkynes via Electrophilic Addition‐Cyclization and Palladium‐Catalyzed Cross‐Coupling

“…This peculiar behaviour suggests that the electrophilic addition to these electron-donating substituted alkynes occurred through a p-methoxy-stabilized open vinyl cation intermediate, instead of, or together with, the predicted thiirenium ion. [12] The open intermediate causes the formation of an E/Z mixture of diastereoisomeric sulfenamides 3, but makes certain the complete regioselectivity of the reaction for the favoured attack of the chloride ion to the more stabilized vinyl cation (Scheme 2).…”

New Class of Biodegradable Polymers Formed from Reactions of an Inorganic Functional Group

“…The 1 H NMR spectrum of the extract before chromatography indicated that approximately 75% of the product was the thiosulfinate (molecule F in Figure 8a) with the remainder mostly composed of molecules G and H. The initial reaction of molecule E with water yielded a sulfenic acid, but sulfenic acids are transient intermediates that very rapidly condense as shown in Figure 8b. 40,47–49 Based on literature precedent, molecule F decomposed via multiple pathways to yield molecule G, molecule H, and a sulfinic acid (molecule I). 48,50–52 Thiosulfinate esters such as molecule F are known oxidation states for cysteine residues and found in nature products such as allicin (a component of garlic; Figure 8c).…”

“…35–40 In a recent article we reported on the synthesis of the first polydiaminosulfides based on the diaminosulfide functional group (R 2 N-S-NR 2 ). 41 The diaminosulfide functional group differs from the sulfenamide functional group in its structure, reactivity, and reaction products.…”

The complete and irreversible conversion of a cis carbon-substituted thiiranium ion into the trans isomer

“…14 When we attempted the synthesis of the t-2-tert-butyl-t-3-phenyl-r-1-methylthiiranium 1 hexachloroantimonate by adding the same electrophile to the (Z)-3,3-dimethyl-1-phenylbut-1-ene at 220 °C, only the trans isomer 2 was obtained. The reaction repeated in CD 2 Cl 2 and monitored by 1 H-NMR at 220 °C confirmed the exclusive formation of the trans thiiranium ion 2.…”

“…Thiiranium ions, the bridged intermediates in the addition of sulfenyl derivatives to alkenes, 1,2 are known to be among the most stable of the iranium ion family with respect to the isomeric open carbonium ions. 1,2 Isolation of these cyclic species 3 and their characterization in the solid state by X-ray structural determination [4][5][6] and in solution mainly by NMR spectroscopy 7,8 together with theoretical ab initio calculations 6,9 have provided detailed information on their structure.…”