5-ENDO CLOSURE OF THE 2-FORMYLBENZOYL RADICAL

The 5-endo cyclization of the 2-formylbenzoyl radical (reaction 2) is shown to be a highly favored process relative to the alternative, 4-ex o-trig ring closure. This evidence comes from product studies, includi ng ESR and laser flash photolysis studies of transient radical interme diates, from a nitroxide trapping measurement of the rate constant for cyclization of the 2-formylbenzoyl radical, viz., k(2) = 2 x 10(8) s( -1) at 45 degrees C, and from the estimated favorable enthalpic change for 5-endo cyclization vs 4-exo-trig cyclization. It is suggested tha t rotation of the formyl group in the initially formed conformer of th e 2-formylbenzoyl radical may be the rate limiting step in this cycliz ation.