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

CD光谱法除了X射线法外，还可用于手性有机化合物绝对构型的非经验测定。本文发展了确定扭π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。(1)光学纯Wieland-Miescher酮的有效制备及其绝对立体化学的CD激子手性方法确认。(2)用X-射线衍射和圆二色性测定了果生褐腐病菌产生的生长自抑制剂--氯青霉素的晶体结构和绝对立体化学。(3)海洋天然强心物质（+）-雄甾醌的全合成及其绝对立体化学的测定。(4)具有多场景发色团的光学活性9，9 '-螺二芴和[6，6]-vespirene衍生物的合成、圆二色性和绝对立体化学。(5)手性螺[3.3]庚烷类化合物的合成及表征 关于我们 通过应用CD激子手性方法终止它们的绝对构型。(6)合成，绝对立体化学，和分离（+）-prehalenaquinone，一个假定的生物合成前体共同卤醌和xestoquinone化合物。(7)用X射线法测定[6，6]-vespirene衍生物的绝对立体化学。(8)测定无环二醇绝对立体化学的圆二色谱法。(9)用圆二色谱理论计算确定天然阻转异构体双黄酮的绝对立体化学。(10)由于双菁染料中的激子耦合而具有独特的紫外可见光和圆二色性行为。(11)用（-）-磺内酰胺拆分羧酸及其绝对构型的测定。(12)用X射线法测定环番的绝对立体化学。(13)萝卜素的结构修正、萝卜下胚轴向光性调节物质及萝卜素类似物的生物活性。(14)链霉菌产乙酰胆碱酯酶抑制剂NK 901093的结构少

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