External Reversal of Chirality Transfer in Photoswitches.

The transfer of stereoinformation is at the heart of asymmetric reactions. By incorporating the natural monoterpene l-menthone into the backbone of a diarylethene, we achieved efficient chirality transfer upon photocyclization, resulting in the preferred formation of one major closed isomer in a diastereomeric ratio (d.r.) of 85:15. More significantly, we were able to completely reverse the diastereomeric outcome of the ring closure simply by altering the chemical environment or the irradiation conditions. As a result, we could selectively accumulate the less favored minor closed isomer, with remarkable d.r. values of >99:1 and 74:26, respectively. Computations revealed that a stability inversion after photocyclization is the basis for the observed unprecedented control over diastereoselectivity.