The chemistry of nitrile sulphides

Chlorocarbonylsulfenyl Chloride Cyclizations Towards Piperidin-3-yl-oxathiazol-2-ones as Potential Covalent Inhibitors of Threonine Proteases

“…35 Nitrile sulphides are short-lived species prone to fragmentation and can take part in further cycloadditions. [36][37][38] After initial unsuccessful attempts to prepare the desired compounds 3a-f, we turned our attention to microwave-assisted report on flow-chemistry synthesis of oxathiazol-2-one in dioxane at 200 °C and residence time of 1 min in a flow reactor reported by Öhrngren et al 39 On this basis, we modified the reaction procedure and dissolved the carboxamides 2a-f (Figure 4) in dry dioxane (27 mL/1 mmol carboxamide), used an excess of solid Na-2 CO 3 (5 eq) and chlorocarbonylsulfenyl chloride (2 eq), and stirred the reaction mixture at 100 °C for 16 h under argon to obtain the desired oxathiazol-2-ones 3a-f ( Figure 4) in 16 to 68% yields (Table 1).…”

12-(N-Methylnitrilium)monocarba-closo-dodecaborate Ylide

“…Numerous nitrilium ylides are known, such as nitrile oxides, 22 sulfides, 23 and ylides carrying carbocyclic 24 or heterocyclic 25,26 anionic groups at the cyano nitrogen, as well as nitriliumphosphane ylides, which are usually used as reactive intermediates generated in situ. 27−29 However, only a limited number of stable nitrilium ylides have been isolated and thoroughly characterized.…”

Nitrile sulfides Part 16. Synthesis of 1,2-benzisothiazoles via nitrile sulfide cycloaddition reactions

“…The formation of nitriles and sulfur as by-products is a common feature of nitrile sulfide reactions and is attributed to desulfurization of the nitrile sulfide competing with the cycloaddition reaction. [19][20][21] Sanders and Grunwell 17 investigated the reaction of with 5-hydroxy-1,4-naphthoquinone with trifluoroacetonitrile sulfide (15, R = CF3), generated from (trifluoroethylimino)sulfur difluoride, and reported the isolation of a single cycloadduct in low yield. This was tentatively assigned the structure 6 on the basis of its mass spectrum.…”

“…[10][11][12][13] Cycloaddition reactions of nitrile imides and nitrile ylides with NQs have also been reported. 14,15 In contrast, much less attention [16][17][18] has been paid to the corresponding reactions with nitrile sulfides (R-CN + S‾), [19][20][21] yet these can provide access to naphtho [2,3-d]isothiazole-4,9-diones (3), a class of compounds for which there appears at present to be no alternative route. An additional incentive to develop this approach is the observation that the isothiazole-fused naphthoquinone aulosirazole (4), which has been isolated from the blue-green alga Aulosira fertilissima, is a solid-tumour selective cytotoxin.…”