The Synthesis of Mercaptans from Olefin Sulfides. II^1,2

Thiiranes

“…/3-Alkoxy mercaptans are obtained by conversion of thiiranes with alcohols in the presence of catalytic quantities of boron trifluoride (213,218). The reaction…”

Chloroperoxidase-induced asymmetric sulfoxidation of some conformationally restricted sulfides

“…Cyclohexene sulfide was obtained from Acros (Geel, Belgium) and distilled prior to use. 16 Ethanol was of spectroscopic grade, HPLC solvents were of HPLC quality (Fisons), and other solvents used were of p.a. quality.…”

Ring opening reactions of thiiranes by alkoxo- and aryloxo-gold(I) complexes

“…It is worthwhile to note that in the case of reactions of unsymmetric thiiranes with alcohols the alkoxo group is reported to attack the secondary or tertiary carbon atom of thiiranes by a proton-induced mechanism. 10 In order to obtain further insights concerning the ring opening reaction, similar reactions with cis-and trans-2-butene sulfide were carried out. As a typical example, the reaction of complex 1c with cis-2-butene sulfide exclusively gave syn-[Au(SCHMeCHMeOPh)(PPh 3 )] 6c in 89% yield, indicating complete inversion at the carbon atom of cis-2-butene sulfide.…”

“…Thiiranes are considered to be versatile starting chemicals toward various sulfur containing compounds 7 and are known to be polymerised by Lewis acids and bases such as TiCl 4 and KOH, 7 and are desulfurised by tertiary phosphines 8 as well as by heating. 9 Ring opening reactions of thiiranes by primary alcohols are also known to be catalysed by BF 3 giving 2-alkoxyethanethiols, 10 though their yields and regio-and stereo-selectivities are poor. Although reactions of transition-metal complexes with thiiranes have also been extensively studied for desulfurisation, 11 the introduction of a sulfur atom into the complex, 12 formation of a thiametallacycle, 13 and cyclooligomerisation, 14 reactions of alkoxo and aryloxo complexes of transition metals with thiiranes are still unexplored so far.…”