The 1,3-dipolar cycloadditions of 1 -azidoadamantane (1) with various olefinic and acetylenic dipolarophiles are described. As olefinic dipolarophiles, strained olefins such as 2-5 and electron-poor olefins such as 11,12, 15, and 18 gave the corresponding adducts, 6-9,16, a retrocycloaddition product 10, and aromatized products 10, 21, and 22. As acetylenic dipolarophiles, phenylacetylene (23) and propargyl alcohol (30) afforded both regioisomers of the adducts 21 and 22 and adducts 31 and 32, respectively. Adamantylacetylene (24) and propicíate esters 27 and 33 gave only 4-substituted triazoles 25,28, and 34. Symmetrical acetylenes 36-39 also gave adducts 40-43. 13C NMR data of some of these triazolines and triazoles were reported also.

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Crown ether catalyzed dehydrobromination of a)-(bromomethylene)adamantane (2) with -BuOK provided a convenient and efficient method of generation of adamantylidenecarbene (1). In the presence of an appropriate olefin, 1 gave the corresponding adamantylidenecyclopropane derivative in 19-92% yields. In the absence of olefins, 1 gave (tert-butoxymethylene)adamantane (12) and bis(adamantylidenemethyl) ether ( 13). Relative reactivities of olefins with 1 were compared with Me2C=C:, and the nature of 1 was discussed on the basis of these data and FMO theory.

such as acrolein, methacrolein, and methyl vinyl ketone occurred smoothly at 80-1 40 "C to afford, regioselectively, adamantane-2-spiro-2'-(1 '-oxa-3'-thiacyclohex-5'-enes) (3a-e) as novel [4 + 21 cycloadducts in good yield. The nature of this cycloaddition is discussed on the basis of kinetics, solvent effects, and FMO theory. I.r.b (cm-')

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