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

除了X射线方法外，圆二色谱方法对于手性有机化合物的绝对构型的非经验测定也是有用的。我们发展了测定扭曲pi-电子体系绝对立体化学的新理论方法，并将其应用于天然产物化学中。(1)光学纯Wieland-Miescher酮的高效制备及其CD激子手性法确证其绝对立体化学；(2)用X射线和CD方法测定果假单胞菌产生的生长抑制剂氯莫尼星的晶体结构和绝对立体化学。(3)强心海洋天然产物(+)-xestoquone的全合成及其绝对立体化学。(4)光学活性9，9‘-螺生物和[6，9’-螺环联苯]的合成、CD和绝对立体化学。(5)手性螺环[3，3]庚烷类化合物和De…的合成通过应用CD激子手性方法更多地终止了它们的绝对构型。(6)合成、绝对立体化学和分离(+)-前卤喹酮，这是一种可能的生物合成前体，类似于卤喹酮和xestoquone化合物。(7)绝对立体化学的测定。6]-维司匹林的X-射线衍生物。(8)测定无环二醇绝对立体化学的CD方法。(9)由CD光谱理论计算确定的天然阿托品双黄酮类的绝对立体化学。(10)双花菁染料中激子耦合引起的独特的紫外可见和圆二色行为。(11)用(-)-舒坦对羧酸的光学拆分和绝对构型的测定。(12)用X-射线方法测定环芳烃的绝对立体化学。(13)萝卜下胚轴向光性调节物质的结构修正(14)淡黄色链霉菌产生的AChE活性抑制剂NK901093的结构。较少

项目成果

N.Harada: "Absolute Stereochemistry of the Halenaquinol Family,Marine Natural Products with a Novel Pentacyclic Skeleton,As Determined by the Theoretical Calculation of Circular Dichroism Spectra" Jounal of the American Chemical Society. 111. 5668-5674 (1

N.Harada：“海萘醌家族的绝对立体化学，具有新型五环骨架的海洋天然产物，由圆二色光谱的理论计算确定”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-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。

A.Lourenco: "The Absolute Stereochemistry at C-12 in 12-Hydroxylate Neo-Clerodane Diterpenoids" (1992)

A.Lourenco：“12-羟基新 Clerodane 二萜中 C-12 的绝对立体化学”(1992)

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。