Previtamin D: Z–E photoisomerization via a Hula-twist conical intersection

Abstract

On photoisomerization of previtamin D – a steroid Z-triene – produced in situ by ring opening of 7-dehydrocholesterol in a cold matrix, it was found in A. M. Müller et al. [Angew. Chem., Int. Ed., 1998, 37, 505–507] that the product (tachysterol) had rotated not only its central double bond but also an adjacent single bond. This is called a Hula twist (HT) due to the alternative description, in which it is just one central CH group that rotates. It was pointed out that the results directly support the calculated molecular structure at a conical intersection, which mediates the Z–E isomerization of polyenes. With a more sophisticated technique, Saltiel et al. (J. Phys. Chem. Lett., 2013, 4, 716–721) confirmed this tachysterol rotamer as the main product but found two additional conformers. They believed to have seen also three previtamin D conformers, suggested to be a result of hot-ground-state reactions from the primary rotamer, and interpreted all tachysterol products to be a result of a double-bond twist (DBT), not a HT. On the basis of published circular dichroism data and consideration of other reactions, it is here shown that under these conditions hot-ground-state reactions are unimportant or even negligible and that there is practically only a single conformer of previtamin D after ring opening. All products can be easily understood on the basis of an HT-type conical intersection, which is thus further supported. Invoking a published pretwist model even rationalizes product ratios. The two twists in HT are concerted. Furthermore HT is fully consistent with the NEER principle (nonequilibration of excited rotamers) and even offers additional possibilities for conformer control.