Synthetic Reactions by Complex Catalysts. IX. Reaction of Thiol with Isocyanide

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Abstract
The reaction of a thiol with an isocyanide proceeds in two directions. In the first reaction (course a), the carbon atom of isocyanide with lone-pair electrons is inserted into the sulfur-hydrogen bond of thiol to produce thioformimidate (I). In the second reaction (course b), isothio-cyanate (II) and the alkane (III) from the alkyl group of thiol are formed. The proportion of the participation of two reactions depends upon the alkyl group of thiol and upon the reaction conditions including whether or not a catalyst is employed. Primary thiol prefers course a to course b, whereas tertiary thiol prefers course b. In the reactions at 15°C, the Group IB and IIB metal compounds, e. g., copper compounds, catalyzed the course a reaction preferably. At higher temperatures, e. g. at 100°C, thiol reacts with isocyanide quite rapidly, even in the absence of a catalyst. However, the catalyst effect favoring course a is seen even in the high-temperature reactions. The mechanism of the reaction, especially course b, has been discussed. Syn-anti structures of thioformimidate were also studied by NMR.

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