Hydroxy thioethers

This reaction is analogous to 10-7. It may be acid (including Lewis acids),base, or alumina catalyzed, occur with electrolysis, and may occur by either an SnI or Sn2 mechanism. Many of the P-hydroxy ethers produced in this way are valuable solvents, for example, diethylene glycol, Cellosolve, and so on. Reaction with thiols leads to hydroxy thioethers. Aziridines can similarly be converted to P-amino ethers. 

A novel approach to the synthesis of desoxy sugars was made by Jeanloz, Prins and Reichstein69 in 1945. In general terms, a 1,2-epoxide was cleaved with sodium thiomethoxide to give a /3-hydroxy thioether which, in turn, was hydrogenolyzed with Raney nickel. It is apparent... 

Cleavage of epoxides with alkylthiotriaikylsilanes. In the presence of Znl, these thiosilanes (R SSiR3) convert epoxides into /J-trimethylsilyloxy thioethers, which can be hydrolyzed to fi-hydroxy thioethers. The regioselectivity can be reversed by use of n-butyllithium as the catalyst. 

Intranwleeulcr cyeUxaHmu The epoxide (1), derived from /roRr-neroUdol in 71 % yield, is cyclized by R-butyllithium in the presence of DABCO to the two isomeric hydroxy thioethers (2) and (3). This reaction is a convenient route to 10-membered sesquiterpenes of the gmnaciane type and may be involved in... 

Peracids are able to form a hydrogen bond with a hydroxy group suitably located with respect to a reaction site. High stereoselectivity can often be expected under these circumstances. Glass et al. made a stereochemical study of oxidation of endo hydroxy thioether (18) (Scheme 1.6). The oxidation by m-chloroperbenzoic acid (mCPBA) is diastereoselective (92% de), while oxidation by i-butyl hypochlorite... 

Hydroxythioethers s. Amino-hydroxy-thioethers, / -Hydroxyethyl — 2-Hydroxythioethers... 

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). 

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