Supramolecular Asymmetric Photochirogenesis with Biopolymers as Chiral Reaction Field

在这项研究中，我提出了一种新的不对称光化学策略或“超分子光致生”的新概念，其中生物分子的手性信息通过手性生物分子宿主与前手性客体底物以及随后的Uni的溶液相超分子相互作用转移到光产物中或在光产物中繁殖。由此产生的主客体复合物的-和双分子光化学反应。采用修饰环糊精、（寡核苷酸）、DNA、RNA和蛋白质作为手性生物分子宿主的所有超分子光致生方法都成功地以良好的光学产率产生了光学活性光产物。因此，在光化学不对称合成中使用手性生物分子的超分子相互作用的最初想法已被证明是一种新的光致氮方法，并有可能扩展到其他超分子系统。更多的论文可以总结如下。第1章主要讨论了(Z)-环辛烯的超分子对映分化光异构化，这些光异构化由几种具有多种发色团的修饰α-、β-和/或γ-环糊精组成并致敏。在取代基、溶剂和温度效应的基础上，详细讨论了包合物的配位行为和随后的对映体分化光敏机理。在第二章中，采用(Z)-环烯向手性(E)-异构体的相同对映分化光异构作为模型系统，评估水溶液中双链DNA的敏化和对映分化能力。对相关核苷和不同序列的单链和双链寡核苷酸的致敏和对映分化能力也进行了检测，以评估DNA对映分化光异构化的起源。一个新的超分子对映分化光异构系统，利用寡核苷酸和DNA，将提出。在第三章和第四章中，研究了一种新的双分子超分子不对称光环二聚2-蒽甲酸酯（AC）与牛和人血清白蛋白（BSA， HSA）的结合，并在水溶液中进行了研究。首先评估了AC在水溶液中与BSA和HSA的结合行为，并在各种条件下进行了超分子对映选择性光环二聚反应，以阐明结合机制和随后的光反应，以获得AC的光学活性光环二聚体

In this study, I have proposed a new strategy of asymmetric photochemistry or a new concept of "supramolecular photochirogenesis," in which the chiral information of biomolecules is transferred to or multiplied in photoproducts through the solution-phase supramolecular interaction of chiral biomolecular hosts with prochiral guest substrates and the subsequent Uni.- and bimolecular photochemical reactions of the resulting host-guest complexes. All of the examined supramolecular photochirogenic approaches, employing modified cyclodextrins, (oligo)nucleotides, DNA, RNA, and protein as chiral biomolecular hosts, were successful in creating optically active photoproducts in good optical yields. Thus, the original idea of using the supramolecular interactions of chiral biomolecules in photochemical asymmetric synthesis has been demonstrated to be useful as a novel photochirogenic methodology, and is potentially extended to the other supramolecular systems. The major findings obtained in this … More thesis may be summarized as follows.Chapter 1 is devoted to the supramolecular enantiodifferentiating photoisomerization of (Z)-cyclooctene included and sensitized by several modified α-,β-, and/or γ-cyclodextrins possessing a variety of chromophores. The inclusion complexation behavior and the subsequent enantiodifferentiating photosensitization mechanism are discussed in detail on the basis of the substituent, solvent, and temperature effects.In Chapter 2, the same enantiodifferentiating photoisomerization of (Z)-cyclooctene to the chiral (E)-isomer was employed as a model system to assess the sensitizing and enantiodifferentiating abilities of double stranded DNA in aqueous solution. The sensitizing and enantiodifferentiating abilities of the relevant nucleosides and single- and double-stranded oligonucleotides of different sequences are also examined to assess the origin of enantiodifferentiating photoisomerization by DNA. A novel supramolecular enantiodifferentiating photoisomerization system, employing oligonucleotides, and DNA, will be proposed.In Chapter 3 and 4, a novel bimolecular supramolecular asymmetric photocyclodimerization of 2-anthracenecarboxylate(AC) bound to bovine and human serum albumin (BSA, HSA) and is investigated in aqueous solutions. The binding behavior of AC to BSA and HSA in aqueous solutions is first assessed and the supramolecular enantioselective photocyclodimerization is performed under a variety of conditions in order to clarify the mechanisms of binding and the subsequent photoreactions to give the optically active photocyclodimers of AC. Less