Synthesis of Adamantane Derivatives. 49. Substitution Reaction of 1-Adamantyl Chloride with Some Trimethylsilylated Unsaturated Compounds

Article abstract of DOI:10.1021/jo01306a004

Catalytic substitution reactions at the adamantane bridgehead were studied by using α,β- and β,γ-unsaturated trimethylsilanes.Treatment of 1-adamantyl (Ad) chloride (1) with allyltrimethylsilane and its heteroanalogues, X=Y-Z-SiMe3, in the presence of Lewis acid as a catalyst gave the products Ad-X-Y=Z, X=Y⁺(Ad)-Z^-, and X=Y-Z-Ad, depending on the attack site of the adamantyl group on each X, Y, and Z atom.Treatment of 1 with (phenylethynyl)trimethylsilane also gave a substituted adamantane in good yield.The substitution reactions of 1 with aryl- and heteroaryltrimethylsilanes under similar conditions occurred at a position distinct from that of acetylation, indicating that adamantylation was not influenced by an electronic effect of the trimethylsilyl group.