Synthesis of Adamantane Derivatives. 59. Reactions of Some Electrophilic Adamantane Derivatives with Unsaturated Organosilanes

Article abstract of DOI:10.1021/jo00138a004

1-Adamantyl acetate (5) and 1-adamantyl silyl ether (12) react with unsaturated organosilanes exactly as the chloride 1 does; the reactions of 5 catalyzed by trimethylsilyl triflate and of 12 catalyzed by TiCl4 with 6 and 7 give the corresponding adamantane-substituted products.Under AlCl3-catalyzed conditions, the reactions of 1-adamantylcarbinyl chloride (17) with 6 and 7 give the products which have a homoadamantane skeleton.Interestingly, the reactions of 1-adamantanecarbonyl chloride (22) with α,β- and β,γ-unsaturated silanes proceed smoothly at -78 deg C (TiCl4) or at room temperature (ZnCl2) while the competitive decarbonylation scarcely takes place.Furthermore, the reactions of 22 with silyl enol ethers are efficiently catalyzed with normal Lewis acids such as SnCl4 to give C-adamantanecarbonylated products.Some adamantane-substituted unsaturated silanes are acetylated under the conditions employed for 22 to give structurally related adamantane derivatives.The aldehyde (53) and ketone (54) show different reactivity to the unsaturated organosilanes; the former reacts with 6, 7, and 25 as usual, but the latter does not.