Cyclization of 5-Hexenyl Radical: Thermodynamics vs. Kinetics

Computations involving the cyclization of the 5-hexenyl radical to produce methylcyclopentane (81%), 1-hexene (17%), and cyclohexane (2%) as a result, proved that the reaction is kinetically rather than thermodynamically controlled. Specifically the stereoelectronic requirement of the addition of the radical center to the alkene in the transition state is the underlying factor of the difference in the ratios of the product and the rate of the reaction because the geometry in cyclized 5-hexenyl radical resembling methylcyclopentane meets the stereoelectronic requirements more readily than cyclized 5-hexenyl radical resembling cyclohexane.