ChemInform Abstract: The Adamantane Rearrangement of syn‐ and anti‐Tricyclo(4.2.1.1.12,5)decane. Part 2. Rearrangements Initiated by Regioselective Formation of Carbocations at C(3) and C(9).

Abstract

ChemInform Abstract Treatment of the exo-alcohol (I) with BF3/Et3SiH (ionic hydrogenation) gives the anti-hydrocarbon (II) as virtually the sole product which is likewise obtained from the endo-alcohol (III) under the same conditions. In addition, (III) is obtained from the alcohols (IVa) or (IVb). On the other hand, the exo/endo alcohols (V) or (VIII) each afford a mixture of the 2-endo-3-endo-(VI) and 2-exo-3-exo-trimethylene-8,9,10-trinorbornanes (VII). Similar results are obtained from the alcohols (IXa) or (IXb). The mechanisms which govern the outcome of these reactions are discussed in detail.