Thiophilic ring opening reactions of 3,3-bis(trifluoromethyl)-5-alkoxy-1,2-dithiolanes under action of nucleophiles

Abstract The reaction of 3,3-bis(trifluoromethyl)-5-alkoxy-1,2-dithiolanes (RO= OEt or OBu-n) proceeds through thiophilic attack of BuLi leading to the formation of ring-opened product BuSCH(OR)CH 2 C(CF 3 ) 2 SLi, which can be converted into the corresponding thiols or sulfides by the reaction with H + or alkyl halide. Interaction of 3,3-bis(trifluoromethyl)-5-n-butoxy-1,2-dithiolane with CF 3 Si(CH 3 ) 3 resulted in unusual reaction leading to the formation of CF 3 SCH(OBu)CH 2 C(CF 3 )=CF 2 ( 7 ). The treatment of 7 with CsF in the presence pentafluoropyridine led to equimolar mixture of 2-n-butoxy-1,1-bis(trifluoromethyl)cyclopropane and 4-(trifluoromethylthio)tetrafluoropyridine (as a result of interception of liberated in this process CF 3 S- anion by pentafluoropyridine).