The Synthesis of 2,4-Dehydrohomoadamantane

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A synthesis of 2,4-dehydrohomoadamantane (I) is described. a) The UV irradiation of a solution of 4-homoadamantene (IV) in xylene containing a small amount of methanesulfonic acid under nitrogen gave a 2: 1 mixture of I and IV after 7 day; this mixture afforded pure I in a 40% isolation yield. b) The oxidation of 4-homoadamantyl hydrazone (XI) by Pb(OAc)4, NiPO, and MnO2 (active) gave a 7–11: 1 mixture of I and IV respectively. It was observed that the ratio of I to IV depends on the reaction temperature, and that the oxidation of XI by Pb(OAc)4 at −78 °C gave thirty times as much I as IV. The addition of MeOH as a proton source reduced the ratio of I to IV in the cases of NiPO and MnO2. The Bamford-Stevens reactions of 4-homoadamatyl tosylhydrazone (II) were effected in aprotic as well as in protic solvents. The ratio of I to IV was inverted under aprotic and protic conditions. The selectivities in the oxidation of XI and the Bamford-Stevens reactions of II were explained by considering the conformations of 4-homoadamantyIidene (XII) and the 4-homoadamantyl cation (VIII).
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