Reaction of methyl azidoformate with norbornene

Abstract
The thermal reaction of methyl azidoformate and norbornene has been found to proceed via 1,3-dipolar-cycloaddition yielding exo triazoline adduct, 15a. Thermal decomposition of the triazoline results in the loss of nitrogen and the formation of at least 5 products. The major products of the thermal decomposition in decalin were 3-carbomethoxy-3-azatricyclo(3.2.1.02,4 exo)octane, 18a, and N-carbomethoxy-2-norbornimine, 20. In addition, syn-2-norbornene-7-methyl carbamate, 21, and 3-carbomethoxy-3-azatricyclo(3.2.1.02,3 endo)octane, 19a, were isolated. The thermal decomposition of the triazoline adduct is considered to proceed by a multi-step mechanism. The first step is considered to involve heterolytic cleavage of the N3—N4 bond togive a zwitterion which may lead to products or rearrange via carbon–carbon bond cleavage to give a diazoalkyl imine.

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