Ungewöhnliche Reaktivität gespannter Brückenkopfderivate

Abstract

Unusual Reactivity of Strained Bridgehead Derivatives The solvolysis of 7,7‐dimethyl‐1, exo‐2‐bis(trifluoromethylsulfonyloxy)norbornane (5) in Et2O/I2Mg and 80% MeOH proceeds with formation of substituted 2‐norbornyl cations, yielding 1, exo‐2‐diiodo‐7,7‐dimethylnorbornane (9) and camphenilone (13), respectively. When the vic‐diiodide 9 is treated with LiAlH4/C6H6 partial epimerization to 1,endo‐2‐diiodo‐7,7‐dimethylnorbornane (12) is observed without reduction; this result is probably due to steric hindrance of the reactants.