Enhanced regioselectivity of Yang photocyclization in the crystalline state

[reaction: see text] In contrast to the solution state, where Yang photocyclization of ketones of general structure 1 leads to equal amounts of cyclobutanols 2 and 3 (by abstraction of HA and HB, respectively), irradiation in the crystalline state is much more regioselective, favoring either 2 or 3 depending on the nature of the substituent X. X-ray crystallography and molecular mechanics calculations reveal the source of this remarkable solid-state regioselectivity.