Organometallic compounds Thioethers

For some time our laboratory has been actively involved in studying the reactivity of mainly cyclopalladated amines and thioethers with disubstituted alkynes. In many cases these reactions afford stable organometallic compounds in which the alkyne has inserted one to three times in the Pd-C bond (Scheme 3). Triple insertions are not discussed herein as they have already been covered in detail elsewhere. ... 

So far we have considered sulfur-containing carbanions obtained by metallation with appropriate bases of a to sulfur atom(s) acidic C-H bonds. For synthetic purposes this method has been by far the most used. Among the variety of other routes to such carbanions [203] we shall consider two methods which seem to be general and promising the reductive lithiation of phenyl thioethers and the thiophilie addition of organometallics to thiocarbonyl compounds (vide infra Section 4.1.2). 

The desulfurization of organosulfur compounds with trivalent organophospho-rus compounds has been studied for more than four decades [118]. A variety of such reagents has been used to convert disulfides to monosulfides, trisulfides to disulfides or monosulfides, /3-keto sulfides to ketones, and sulfenimides to amines. They have also been used to remove sulfur from thioethers, thiols, and organometallic dithiocarboxylates, and oxygen from sulfones. 

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