Mechanism of the [2 + 2] photocycloaddition of fullerene C60 with styrenes

Article abstract of DOI:10.1021/jo0006223

Stereochemical studies on [2 + 2] photoaddition of cis-/trans-4-propenylanisole (cis-1 and trans-1) and cis-1-(p-methoxyphenyl)ethylene-2-d₁ (cis-3-d₁) to C₆₀ exhibit stereospecificity in favor of the trans-2 cycloadduct in the former case and nonstereoselectivity in the latter. The observed stereoselectivity in favor of the cis-6-d₃ [2 + 2] diastereomer by 12% in the case of the photochemical addition of (E)-1-(p-methoxyphenyl)-2-methyl-prop-1-ene-3,3,3-d₃ (trans-5-d₃) to C₆₀ is attributed to a steric kinetic isotope effect (k(H)/k(D) = 0.78). The loss of stereochemistry in the cyclobutane ring excludes a concerted addition and is consistent with a stepwise mechanism. Intermolecular secondary kinetic isotope effects of the [2 + 2] photocycloaddition of 3-d₀ vs 3-d₁, and 3-d₆ as well as 5-d₀ vs 5-d₁, and 5-d₆ to C₆₀ were also measured. The intermolecular competition due to deuterium substitution of both vinylic hydrogens at the β-carbon of 3 exhibits a substantial inverse α-secondary isotope effect k(H)/k(D) = 0.83 (per deuterium). Substitution with deuterium at both vinylic methyl groups of 5 yields a small inverse k(H)/k(D) = 0.94. These results are consistent with the formation of an open intermediate in the rate-determining step.