Studies on Noble Methodology of Supramolecular Photochirogenesis with Biopolymers as a Chiral Reaction Media

近年来，利用各种超分子进行不对称光化学的新方法受到越来越多的关注。在本文中，我们将介绍定制生物分子的超分子不对称光致光合作用（SMAP）的新策略和最新成果。生物聚合物，特别是蛋白质，具有客体的手性结合袋，作为潜在的手性反应腔和/或SMAP领域特别令人感兴趣，尽管这种方法尚未得到广泛的研究。血清白蛋白是最丰富的水溶性血浆蛋白，其转运疏水化合物。我们采用牛和人血清白蛋白（BSA和HSA）作为手性超分子宿主，2-蒽甲酸酯（AC）作为底物。在HSA存在的缓冲水溶液中进行AC的光环二聚反应，得到了对映选择性高达90%的[4+ 4]环二聚体。催化抗体是近年来研究热反应的重要工具之一。催化抗体具有AC环二聚体的手性结合袋，作为SMAP的潜在手性宿主尤其令人感兴趣，尽管这种方法尚未得到广泛的研究。在这项研究中，我们首次证明了使用催化抗体作为定制的手性反应场的超分子光致光作用。

Increasing attention has recently been directed toward the new methodology of asymmetric photochemistry using various supramolecules. In this paper, we will present the novel strategy and recent results of supramolecular asymmetric photochirogenesis (SMAP)with tailor-made biomolecules. The biopolymers, especially proteins, possessing chiral binding pockets for guest, are of particular interest as potential chiral reaction cavities and/or fields for SMAP, although such an approach has not extensively been investigated. Serum albumins are the most abundant and well-characterized water-soluble plasma proteins, which transport hydrophobic compounds. We have employed Bovine and Human Serum Albumin (BSA and HSA)as a chiral supramolecular host and 2-anthracenecarboxylate (AC)as a substrate. The photocyclodimerization of AC was performed in aqueous buffer solutions in the presence of HSA to give the [4+ 4] cyclodimers with high enantioselectivities of up to 90%ee.Recently catalytic antibody is one of the most powerful and vital tools for thermal reactions. The catalytic antibody possessing chiral binding pockets for AC cyclodimers, are of particular interest as potential chiral hosts for SMAP, although such an approach has not extensively been investigated. In this study, we have demonstrated first supramolecular photochirogenesis using catalytic antibody as tailor-made chiral reaction fields.