FUNCTIONALIZATION REACTIONS OF TRICYCLO[5.2.1. 4, 10]DECANE . TRICYCLO[5.2.1.04,10]DECANE TOADAMANTANE REARRANGEMENT

Treatment of tricyclo[5.2.1.04,10]decane (1) with carbomethoxynitrene leads chiefly to insertion into the tertiary C-H bonds (when evaluated on a per-hydrogen basis). A reactivity ratio of 4.0:3.8:1.0 for the tertiary apical, tertiary nonapical, and methylene positions is observed. Similarly, chromyl acetate oxidation of 1 results in preferential attack at tertiary carbons. However, the tertiary apical position does not undergo oxidation. These contrasting features are discussed. Exposure of 1 to aluminum chloride in refluxing hexane leads to adamantane. Treatment of several tricyclo[5.2.1.04,10]decanols with fluorosulfonic acid, followed by aqueous quenching, yields 1-adamantanol. These transformations are accommodated by a scheme involving nonbridgehead carbonium ions which rearrange only by 1,2-alkyl shifts. © 1969, American Chemical Society. All rights reserved.