R. Yamaguchi, T. Katsushima, M. Kawanisi
Aug 1, 1975
Citations
0
Influential Citations
9
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The synthesis of several 2-mono- and 2,4-di-substituted homoadamantane derivatives is described. The photobromination of 2,4-dehydrohomoadamantane (I) at −78 °C gave e,a- and e,e-2,4-dibromohomoadamantanes (IIa and IIb). The treatment of a mixture of IIa and IIb with t-BuOK in HMPT gave e-2-bromohomoadamant-4-ene (IV) in an 84% yield. The methanolysis and hydrolysis of IV gave e-2-methoxyhomoadamant-4-ene (V) and e-2-hydroxyhomoadamant-4-ene (VI), with a retention of the configuration, in 90 and 99% yields respectively. The oxidation of VI with the CrO3-pyridine complex gave homoadamant-4-en-2-one (VII) in a 94% yield. The reduction of VII with LiAlH4 gave a-2-hydroxyhomoadamant-4-ene (VIII). The catalytic hydrogenations of VI, VII, and VIII gave e-2-hydroxyhomoadamantane (IX), homoadamantan-2-one (X), and a-2-hydroxyhomo-adamantane (XI) respectively. The possibility that a homoallylic cation (XII) intervenes in the solvolysis of IV is proposed.