Competition between cyclization, cleavage, and reverse hydrogen transfer in 1,4-hydroxybiradicals: crystal structure--solid state reactivity correlations
[reaction: see text] To provide experimental evidence on the relationship between stucture and reactivity in 1,4-hydroxybiradical intermediates, the Norrish type II photochemistry of a homologous series of spirobenzoyladamantane derivatives was investigated in the crystalline state and the outcome correlated with the structures of the compounds as determined by X-ray crystallography. The results provide an unusually detailed and compelling picture of the geometric factors responsible for the partitioning of these reactive intermediates among cleavage, cyclization, and reverse hydrogen transfer.
Cheung
E
Department of Chemistry, University of British Columbia, Vancouver, Canada.
Netherton
MR
Scheffer
JR
Trotter
J