Thiolysis of epoxides

P-Hydroxy thioethers can be obtained in good yields via the thiolysis of epoxides [86] using catalytic amounts of BiCl3 (10 mol%) [86a] or Bi(OTf)3 xH20 (1 mol%) [45]. It is noteworthy that this reaction was achieved in the presence of tetrabutylphosphonium bromide which allows the recycling of the catalyst (Equation 42). 

Scheme 23. Reaction for Thiolysis of enantiomerically pure epoxide mediated by 51,...

FringuelU, F., Pizzo, F., Vittoriani, C. and Vaccaro, L. (2006) Polystyrene-supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene as an efficient and reusable catalyst for the thiolysis of 1,2-epoxides under solvent-free conditions. European Journal of Organic Chemistry, 1231-1236. 

The formation of P-bromohydrins and p thioalcohols from epoxides has also been reported. For example, Shibasaki has shown that the heterobimetalhc gallium lithium BINOL complex (12.138) is a good catalyst for nucleophilic ringopening of epoxides, including the use of thiols. Cyclohexene epoxide (12.116) is converted into the sulfide (12.141) with very good enantioselectivity. Indium complexes of bipyridine (12.126) are very active catalysts in the thiolysis of meso-epoxides providing between 92 and 96% ee in the reaction of ds-stilbene oxides with a range of aromatic and aliphatic sulfides. ... 

Fringuelli, R, Pizzo, R, Tortoioli, S. and Vaccaro, L., Thiolysis of alkyl- and aryl-1,2-epoxides in water catalyzed by InCb, Adv. Synth. CataL, 2002,344,379—384. 

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