Reaction of unsaturated compounds with ethyl benzenesulfenate and trimethylsilyl isothiocyanate

Abstract

A new method for the synthesis of thiocyanato and isothiocyanatoalkyl phenyl sulfides by the reaction of unsaturated compounds with ethyl benzenesulfenate and trimethylsilyl isothio cyanate has been suggested. Regio and stereoselectivity of the reaction was studied, having taken alkenes, dienes, and alkynes as examples.

Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P‐ and As‐Containing Analogues

“…Nevertheless, the available experimental results indicate that the thermodynamic factor governs the formation of the products with these electrophiles. Indeed, the formation of the thermodynamically favoured R−NCX isomers was observed in the following reactions: the [NCO] − ion with P‐ [113] or B‐electrophiles, [114] [NCO] − and [NCS] − ions with Ge‐centred electrophiles, [115] and silylation of all the [NCX] − anions [116–119] …”

“…Indeed, the formation of the thermodynamically favoured RÀ NCX isomers was observed in the following reactions: the [NCO] À ion with P- [113] or B-electrophiles, [114] [NCO] À and [NCS] À ions with Ge-centred electrophiles, [115] and silylation of all the [NCX] À anions. [116][117][118][119]…”

Catalyst‐Free Isothiocyanatoalkylthiation of Styrenes with (Alkylthio)pyrrolidine‐2,5‐diones and Trimethylsilyl Isothiocyanate

“…We also have developed some useful difunctionalization reactions of alkenes 16. To the best of our knowledge, only one reference was reported on the isothiocyanatophenylthiation of alkenes in which ethyl benzenesulfenate alone was used as the phenylthiolating reagent,17 and mixtures of isothiocyanates and thiocyanates were found in the reaction system. Therefore, the diversity of compounds is greatly limited through this method because it is difficult to prepare this kind of alkylthiolating reagent.…”

Mild and convenient one-pot synthesis of 2-amino-1,3,4-thiadiazoles using trimethylsilyl isothiocyanate (TMSNCS)

“…[8][9][10][11] Among the silicon reagents, we particularly focused on TMSNCS due to its wide synthetic applications. TMSNCS is a useful and important reagent for the thiocyanation or isothiocyanation of various alkyl halides, 12 acetals, 13 aldehydes, 13 olefines, 14,15 aziridines, 16 oxiranes 16 and aromatic hydrocarbons. 17 We previously reported the one-pot, convenient synthesis of mercapto-1,2,4-triazoles using TMSNCS.…”