Synthesis of Novel, Highly Reactive Sulfur-containing Species by Taking Advantage of Steric Protection

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We have synthesized two types of highly reactive organosulfur species by taking advantage of steric protection due to bulky substituents such as 2,4,6-tri-t-butylphenyl (Mes^*) and 4-t-butyl-2,6-bis[(2,2",6,6"-tetrametyl-m-terphenyl-2'-yl)methyl]phenyl(Bmt). Reaction of stable thioaldehyde Mes^*CHS, synthesized by us as the first stable thioaldehyde, with N-bromo- or N-chlorosuccinimide gave the corresponding thioacyl halides Mes^*C(=S)X(X=Br,Cl), which reacted with alcohols, thiols or amines to afford thioesters, dithioesters or thioamides. BmtLi attacked on the sulfur of CS_2 (thiophilic reaction) to produce highly reactive anionic species having carbene character, (BmtS)(LiS)C : (1),which was in equiliprium with dimeric species, (BmtS)(LiS)C=C(SLi)(SBmt) (2).Anionic species 1 and 2 were also formed when HC(=S)(SBmt) was deprotonated with lithium tetramethylpiperidide and quenched with a variety of alkyl halides. Anion 1 was stabe at -78℃ but decomposed into C=S and BmtSLi at -30℃. This represents a novel method for the generation of C=S.