Silicon-containing $1{,}3$-alkenynes and more unsaturated compounds

The methods of synthesis and characteristic features of the reactivity of silicon-containing alkenynes are treated systematically and surveyed for the first time. It is shown that the carbon–carbon double bonds are reactive in the reactions of silahydrocarbons and their functional derivatives containing the $\equiv\mathrm{Si}-\mathrm{C} \equiv\mathrm{C}-\underset{|}{\mathrm{C}}=\mathrm{C}\!\!<$ fragments. Only aluminium, boron, and tin hydrides as well as certain weak electrophiles add preferentially or exclusively to the triple bond. The absence of a dependence of the mode of addition on the polarity of the unsaturated compound and the other reactant indicates orbital control in the reactions investigated. Studies of the dependence of the mode of reaction (addition, desilylation, reactions of functional groups) on the structure of the silicon-containing alkenynes, the nature of the other reactant, and the experimental conditions served as a basis of the development of methods for the introduction of functional groups into the alkenynes and of silyl protecting group method in the chemistry of acetylenic compounds and have demonstrated the extensive possibilities of the application of these procedures in the stereocontrolled synthesis of natural products and their synthetic analogues. The bibliography includes 346 references.