Synthesis, reactions, and interconversions of some 2-(trimethylsilyl)ethyl substituted sulfur compounds

Abstract

In an effort to probe the compatibility of the 2-(trimethylsilyl)ethyl sulfur moiety with standard organosulfur transformations, several 2-(trimethylsilyl)ethanethiol derivatives have been prepared in excellent yield. Thus 2-(trimethylsilyl)ethanethiol (1) and 2-(trimethylsilyl)ethyl disulfide (4) and its corresponding thiosulfinate 9 and thiosulfonate 10 have been synthesized. One method of formation of 4 involves the breakdown of a 1-(trimethylsilyl)ethyl unit while the 2-(trimethylsilyl)ethyl fragment survives. Oxidation of 4 or 9 to 10 did not proceed efficiently with common reagents, but proceeded well with an iodine/water system. 2-(Trimethylsilyl)ethyl sulfide (11a) and its oxides (13, 14) were also prepared in good yield. Sulfoxide 13 and 2-(trimethylsilyl)ethyl tert-butyl sulfoxide 15 were shown to be good precursors to 2-(trimethylsilyl)ethanesulfinyl chloride (16). (Trimethylsilyl)methyl sulfine reacted with 16 in an inefficient manner to give thiosulfonates 10, 19, and 20. 2-(Trimethylsilyl)ethanesulfenyl chloride could be generated and captured by addition across cyclohexene. The reaction of thiosulfinate 9 with several thiosilanes is an excellent method for the synthesis of 2-(trimethylsilyl)ethyl containing mixed disulfides.