Lumisterol to Tachysterol Photoisomerization in EPA Glass at 77 K. A Comparative Study.

We present a comparative study of the photoisomerizations of lumisterol (Lumi), previtamin (Pre), and provitamin D (Pro) to tachysterol (Tachy) at 77 K in EPA (5:5:2 ether, isopentane, and ethanol by volume) glass. Fluorescence, fluorescence excitation, and UV spectra, measured in the course of these reactions, were analyzed using singular value decomposition with self-modeling (SVD-SM). This represents an extension of previous work that led to the conclusion that in the EPA glass Pre exists as an s-cis,s-cis-conformer (cZc-Pre) which gives, exclusively, an unstable s-cis,s-cis-conformer of Tachy (cEc-Tachy) and Pro gives mainly the tEc-Tachy, that corresponds to a stable s-trans,s-cis-conformer. ( Redwood , C. ; et al. J. Phys. Chem. Lett. 2013 , 4 , 716 - 721 . ) The surprising result was that the major Pre photoproduct from Pro also has a tZc-Pre conformation instead of the expected cZc-Pre conformation. Accordingly, the Pre to Tachy cis-trans photoisomerization proceeds via a conformer specific one-bond-twist (OBT) process as proposed by Havinga ( Maessen , P. A. ; et al. Angew. Chem. Int. Ed. Engl. 1983 , 22 , 718 - 719 . Maessen , P. A. ; et al. Angew. Chem. Int. Ed. Engl. 1983 , 22 , 994 - 1004 . Maessen , P. A. Ph.D. Thesis, State University at Leiden, Leiden, The Netherlands, 1983. ). The role of the EPA glass in controlling conformer distributions and reaction outcomes is further explored by the extension of the studies to Lumi, whose structure differs substantially from that of its stereoisomer, Pro. Initially, the light-induced conrotatory ring openings of Pro and Lumi are expected to give cZc-Pre conformers that differ in the relative orientation of the double bond dihedral angles that define the chiral axis of the triene moiety: (-)cZ(-)c-Pre and (+)cZ(+)c-Pre, respectively. In the case of Pro, much of the cZc-Pre proceeds to tZc-Pre, the precursor of tEc-Tachy. In contrast, we show that under the same conditions most cZc-Pre formed from Lumi retains the cZc-conformation and isomerizes to cEc-Tachy. cZc-Pre from Lumi was not detected by fluorescence, but UV absorption measurements establish its formation as an essential intermediate to Tachy. Aided by theoretical calculations of conformer UV and CD spectra, we conclude that fluorescent thermodynamic Pre and nonfluorescent Pre from Lumi are both (+)cZ(+)c-Pre conformers. They differ in the orientation of the OH in the A ring, pseudoequatorial in the former and pseudoaxial in the latter. The most likely major photochemical sequences starting from Pre and Lumi are (+)cZ(+)c-Pre-eq-OH → (+)cE(+)c-Tachy-eq-OH and Lumi → (+)cZ(+)c-Pre-ax-OH → (+)cE(+)c-Tachy-eq-OH.