Photolysis of chiral 1-pyrazolines to cyclopropanes:: Mechanism and stereospecificity

The photodenitrogenation of chiral trisubstituted 1-pyrazolines has been studied by laser flash photolysis. These experiments have permitted the detection of two transients that have been assigned, for each pyrazoline, to the trimethylene-type diradical resultant from the extrusion of nitrogen (lifetime tau = 0.1-0.8mus) and to the pyrazoline triplet (r < 9 ns), respectively. The efficiency of the photosensitization process has been evaluated by determination of the corresponding quenching rate constant in each instance. Theoretical calculations support a mechanistic pathway involving a trimethylene radical as intermediate that rapidly evolves to the corresponding cyclopropane derivative. The cyclopropane ring-closure is predicted to be faster than rotation around the C-C bond, thus accounting for the observed stereospecificity.