Photochemistry of 9-methylbicyclo[3.3.1]nonyl aryl ketones — A novel 1,5-disproportionation of 1,4-hydroxy biradicals and asymmetric induction using the solid-state ionic chiral auxiliary method

Abstract

A novel 1,5-disproportionation reaction has been discovered for 1,4-hydroxy biradicals derived from the photolysis of 9-methylbicyclo[3.3.1]nonyl phenyl ketones (1), which undergo mainly Yang cyclization both in solution and the solid state. By applying the solid-state ionic chiral auxiliary method of asymmetric synthesis to the Yang cyclization, enantiomeric excesses as high as 95% were achieved at high reaction conversions. The origin of the reaction selectivity is discussed with the help of X-ray crystallography. In addition, the solid-state photoreaction of ketone 1b was found to occur in a single crystal-to-single crystal fashion.Key words: photochemistry, 1,4-hydroxy biradical, disproportionation, asymmetric induction, ionic chiral auxiliary, single crystal-to-single crystal reaction.