Circular Dichroism of Twisted pi-Electron Systems and Its Application to Natural Products Chemistry

扭曲π电子体系的圆二色性及其在天然产物化学中的应用

• 批准号: 01470026
• 负责人: HARADA Nobuyuki
• 金额: $ 4.61万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470026/
• 关键词: CD exciton chirality method; twisted pi-electron system; absolute stereochemistry; absolute stereochemistry of acyclic glycols; cardiotonic marine natural product; natural atropisomer biflavone; phototropism-regulating substances; AChE activity inh

The CD spectroscopic method is useful for non-empirical determination of the absolute configuration of chiral organic compounds, in addition to the X-ray method. We have developed the new theoretical method for determination of the absolute stereochemistry of twisted pi-electron systems, and have applied it to the natural products chemistry.(1) Efficient preparation of optically pure Wieland-Miescher ketone and confirmation of its absolute stereochemistry by the CD exciton chirality method.(2) Crystalline structure and absolute stereochemistry of chloromonilicin, a growth selfinhibitor produced by Monilinia fructicola, determined by X-ray and CD methods.(3) Total synthesis of (+)-xestoquinone, an cardiotonic marine natural product, and determination of its absolute stereochemistry.(4) Synthesis, CD, and absolute stereochemistry of optically active 9, 9'-spirobifluorene and[6, 6]-vespirene derivatives with polyscene chromophores.(5) Synthesis of chiral spiro[3.3]heptane compounds and de … More termination of their absolute configuration by application of the CD exciton chirality method.(6) Synthesis, absolute stereochemistry, and isolation of (+)-prehalenaquinone, a putative biosynthetic precursor common to halenaquinone and xestoquinone compounds.(7) Determination of the absolute stereochemistry of[6, 6]-vespirene derivatives by the X-ray method.(8) A CD method for determination of the absolute stereochemistry of acyclic glycols.(9) Absolute stereochemistry of natural atropisomer biflavone as determined by the theoretical calculation of CD spectra.(10) Unique ultraviolet-visible and circular dichroism behavior due to exciton coupling in a biscyanine dye.(11) Optical resolution of carboxylic acids by use of (-)-sultam and determination of absolute configuration.(12) Determination of the absolute stereochemistry of cyclophanes by the X-ray methods.(13) Revision of the structure of raphanusanins, phototropism-regulating substances of radish hypocotyls, and biological activity of raphanusanin analogus.(14) Structure of NK901093, an AChE activity inhibitor produced by Streptomyces lavendulae. Less

CD光谱法对Ciral Organic Chipsounds Ay方法的绝对构型的非经验确定为基础。并将其应用于cd的cd型果质素食，并将其用于（1）TE立体化学方法[6，6]带有多晶状体化合物的螺旋烯衍生物。前体奎因化合物。 。

项目成果

N. Harada: ""Optical Rotation and CD Spectroscopy", Chapter 5" Yuuki Kagaku Jikken no Tebiki'. Kagaku Dojin. 85-102 (1989)

N. Harada：““旋光和 CD 光谱”，第 5 章“Yuuki Kagaku Jikken no Tebiki”。

N.Harada: "A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols.1.Application of the CD Exciton Chirality Method to Acyclic 1.3-Dibenzoate Systems" Journal of the American Chemical Society. 113. 3842-3850 (1991)

N.Harada：“用于测定无环乙二醇绝对立体化学的 CD 方法。1.CD 激子手性方法在无环 1.3-二苯甲酸酯体系中的应用”美国化学会杂志。

N.Harada: "A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols.1.Application of the CD Exciton Chirality Method to Acyclic 1,3ーDibenzoate Systems." Journal of the American Chemical Society. 113. (1991)

N.Harada：“测定无环乙二醇绝对立体化学的 CD 方法。1.CD 激子手性方法在无环 1,3-二苯甲酸酯体系中的应用。”美国化学会杂志 113。

N.Harada: "Stereochemistry of Chloromonilicin,a New Antifungal Metabolite Produced by <Monilinia Fruticola>___ー,as Determined by XーRay Crystallographic and CD Spectroscopic Methods." (1991)

N.Harada：“由 X 射线晶体学和 CD 光谱方法测定的 <Monilinia Fruticola>___ 产生的新型抗真菌代谢物氯莫尼霉素的立体化学”(1991)。

N.Harada,H.Uda,K.Nakasuji,I.Murata: "Interchromophoric Homoconjigation Effect and Intramolecular Charge-transfer Transition of the Triptycene System Containing a Tetracyanoquinodimethane Chromophore" Journal of the Chemical Society,Perkin Trans.II. 1449-1

N.Harada，H.Uda，K.Nakasuji，I.Murata：“含有四氰基醌二甲烷发色团的三蝶烯系统的发色团间同缀合效应和分子内电荷转移跃迁”化学会杂志，Perkin Trans.II。