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

除X射线方法外，CD光谱法可用于非经验确定手性有机化合物的绝对构型。 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 excitingon chirality method.(2) Crystalline structure and absolute stereochemistry of chloromonilicin, a growth selfinhibitor produced （3）（3）（+） - Xestoquinone的总合成，Xestoquinone，一种心脏元素海洋天然产物，并确定其绝对立体化学化学。（4）合成，CD，CD和绝对立体化学的腐蚀性9，9'-SpirobifluoreNe和[6''s-Spireene andiv and consotonic notherage。 chromophores.(5) Synthesis of chiral spiro[3.3]heptane compounds and de … More termination of their absolute configuration by application of the CD exciting method.(6) Synthesis, absolute stereochemistry, and isolation of (+)-prehalenaquinone, a putative biosynthetic precursor common to halenaquinone and xestoquinone compounds.(7) Determination of the absolute通过X射线方法的立体化学化学化学化学化学化学化学。（8）一种CD方法，用于确定无循环的绝对立体化学的CD方法。（9）自然立体化学的绝对立体化学方法是通过自然萎缩型双酮的绝对定位化学通过CD的理论来确定的（10）独特的Ultortiole and Cripitifile and Criciolial-visicioLERTIOL-diorsile-visicioLERTIOL-difter-visicioLERTIOL-VISROLID-VISTROLIEL。 （11）通过使用（ - ） - 苏丹和确定绝对构型的羧酸的光学分辨率。（12）确定X射线方法通过X射线方法确定环形烷的绝对立体化学化学。 raphanusanin emalogus。（14）NK901093的结构，这是由Lavendulae链霉菌产生的ACAE活性抑制剂。较少的

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。