Synchronous enantiomeric enrichment of both reactant and product by absolute asymmetric synthesis using circularly polarized light. Part 3. Numerical simulation and experimental verification of the reversible asymmetric photoisomerization between methyl norbornadiene-2-carboxylate and methyl quadricyclane-1-carboxylate

Abstract

In the first paper of this series, we proposed a new absolute asymmetric synthesis (NAAS) with circularly polarized light (CPL), which can be classified into two subcategories: (a) reversible NAAS (CPL excites both the reactant and product), (b) irreversible NAAS (the reactant only is excited by CPL). In the present paper we deal with reversible NAAS. The numerical simulations, which are based upon the results of the preceding paper of this series, are performed. Using the reversible photoisomerization between methyl norbornadiene-2-carboxylate (I) and methyl quadricyclane-1-carboxylate (II), it was experimentally verified that the enantiomeric excesses (ee's) of both the reactant and product were critically dependant not only on the anisotropy factors (g = Δε/ε) of both components, but also on the relative quantum yields of the forward and reverse reactions. In the case of reversible NAAS, the ee of the reactant and the product will concurrently increase according to the conversion, and attain appreciable values at the photostationary state if we appropriately select the system and the CPL-irradiation wavelength in such a way that if the g factors of the product and the reactant are large enough, the sign of the g factor of the product is opposite to that of the reactant, and the photochemical equilibrium constant K is less than unity.