α,β-Unsaturated nitroso system-I : The generation and transformations of ω-nitroso camphene

Abstract

MO calculations predict a pronounced 1,4-dipolar character for the α,β-unsaturated nitroso synthon, much above that for traditional systems like the α,β-unsaturated Nitro and α,β-unsaturated carbonyl. The work on ω-nitroso camphene-generated from inter alia ω-Nitrocamphene 3 is in agreement with the expectations. Thus, the 3 → tricyclene aldehyde 4 change is rationalized on the basis of a σ shift and the 5 → 20 and 6 → 21 changes highlight the overwhelming influence of the α,β-unsaturated nitroso synthon over even the enol ether and enamine functions present in 5 and 6. Amongst other noteworthy features are the deep seated 3 → 8 rearrangement and the preparation and transformation of the extraordinarily stable and the first reported bridgehead nitrile oxide 14.