Development of CD Method and Applications to Stereochemistry

CD光谱学方法与X射线结晶学方法相结合，可用于确定手性有机化合物的绝对立体结构。作为CD激子手性方法的推广，我们提出了一种非经验确定扭曲pi-电子体系绝对立体化学的新理论方法。用pi-电子SCF-CI-DV分子轨道方法对CD光谱进行了理论计算，并测定了下列生物活性天然产物和合成的手性有机化合物的绝对立体结构。1.阐明了适合于CD激子手性方法应用于低聚糖的发色团的电子结构。2.用CD和X-射线方法测定了12-羟基新核桃烷二萜中C-12位的绝对立体化学。3.合成了具有分子不对称性的手性烯烃，并对其绝对立体结构进行了…分析CD法测定的白藜芦醇含量较高。4.研究了手性桥联联苯的CD和绝对立体化学。5.我们发现一种手性双花菁染料在UV-Vis吸收和CD光谱中表现出异常强烈的激子分裂，6.建立了CD激子法测定无环1，3-二苯甲酸酯体系的绝对立体化学。d阐明了其独特的激子耦合行为的起源和性质。7.合成了具有9，9‘-螺联荧骨架的手性螺环芳香族化合物，并用CD法测定了它们的绝对立体结构。8.首次测定了阿托品异构体双黄酮(-)-4’，4‘’‘，7，7’‘-tetra-O-methylcupressuflavone，的绝对立体化学通过CD光谱的理论计算。9.发展了一种用于光学拆分和X射线结晶学测定手性羧酸绝对立体化学的手性探针。10.通过X射线结晶学和CD光谱研究，修正了以前错误地根据化学关联确定的(8)和(10)-对环番羧酸的绝对立体化学。较少

The CD spectroscopic method, together with the X-ray crystallographic method, is useful for determination of the absolute stereostructure of chiral organic compounds. We have proposed, as an extension of the CD exciton chirality method, a new theoretical method for nonempirical determination of the absolute stereochemistry of twisted pi-electron systems. The CD spectra can be theoretically calculated by the pi-electron SCF-CI-DV molecular orbital method, and we have determined the absolute stereostructures of the following biologically active natural products and synthetic chiral organic compounds with theoretical interest.1.The electronic structure of rho-methoxycinnamate chromophore suitable for application of the CD exciton chirality method to oligosaccharides was clarified.2.absolute stereochemistry at C-12 in 12-hydroxylated neo-clerodane diterpenoids was determined by CD and X-ray methods.3.Chiral olefins with molecular asymmetry were synthesized, and their absolute stereostructu … More res were determined by the CD method. the kinetics and mechanism of their photo and thermal racemization were also clarified.4.CD and absolute stereochemistry of chiral bridged biphenyls were studied.5.We found that a chiral biscyanine dye exhibits unusually strong exciton split in UV-VIS absorption and CD spectra, and the origin and nature of its unique exciton coupling behavior were clarified.6.We developed a CD exciton method for determination of the absolute stereochemistry of acyclic 1,3-dibenzoate systems.d the origin and nature of its unique exciton coupling behavior were clarified.7.Chiral spiroaromatic compounds with 9,9'-spirobifluorene skeleton including[6,6]-vespirene were synthesized and their absolute stereostructures were determined by the CD method.8.We have succeeded in the first determination of the absolute stereochemistry of atropisomeric biflavone, (-)-4',4''',7,7''-tetra-O-methylcupressuflavone, by theoretical calculation of CD spectra.9.A chiral probe useful for optical resolution and X-ray crystallographic determination of the absolute stereochemistry of chiral carboxylic acids was developed.10.We revised, by X-ray crystallographic and CD spectral studies, the absolute stereochemistry of (8)-and(10)-paracyclophane carboxylic acids previously erroneously determined on the basis of chemical correlation. Less