Theoretical Development of the CD spectroscopic Method and Application to Bio-organic Science

CD光谱法的理论发展及其在生物有机科学中的应用

基本信息

批准号：
07408032
负责人：
HARADA Nobuyuki
金额：
$ 3.97万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1998
项目状态：
已结题

项目摘要

(1). Chiral Phthalic Acid Amide, a Chiral Auxiliary Useful for Enantiomer Resolution and X-Ray Crystallographic Determination of the Absolute Stereochemistry of Alcohols.(2). A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols. 2. Application of the CD Exciton Chirality Method to Acyclic 1,2-Dibenzoates Systems.(3). The CD Exciton Chirality Method and Benzoylation of Sterically Hindered alpha-Glycol by Trans-Esterification : Forskolin Case.(4). Lipase-Catalyzed Kinetic Resolution of Cyclobutylmethanols and Determination of Absolute Stereochemistry by X-Ray Analysis.(5). Enantioresolution and Absolute Stereochemistry of 3,3'-DiacetyI-4,4', 6,6'-tetramethoxy- 2,2'-biphenyldiol.(6). Total Synthesis and Absolute Stereochemistry of Natural Atropisomer of Biflavone, [CD(+)362.0]-(-)4', 4''', 7,7"-Tetra-O-methylcupressuflavone.(7). Application of the CD Exciton Chirality Method to Chiral 1,2-Diamines. Use of C2v-symmetrical 2,3-Naphthalenedicarboximido Chromophore … More .(8). Enantioresolution and Absolute Stereochemistry of 2-(l-Naphthyl)propane-l, 2-diol and Related Compounds. The method using chiral phthalic acid amides was applied to make the enantioresolution of 2-(l-naphthyl)propane-l, 2-diol giving enantiopure (-)-diol, the S absolute configuration of which was unambiguously determined by X-ray crystallography of its (-)-p-bromobenzoate. The S absolute configurations of (+)-2-methoxy-2-(1-naphthyl)propionic acid and related compounds were also determined by chemical correlation to (S)-(-)-diol.(9). New Strategy for Determining the Absolute Stereochemistry of Mono-Functional Compounds by the CD Exciton Chirality Method. The CD exciton chirality method has been extensively applied to various natural products and chiral synthetic compounds to determine their absolute configurations in a nonempirical manner. However, application of the CD exciton chirality method has been limited to chiral compounds with two or more functional groups, because exciton CD Cotton effects are observable only for the interaction between two or more chromophores. This has been a weak point of the CD exciton chirality method, and therefore it has never been applied to mono-functional chiral compounds. We reported a new strategy for determining the absolute configuration of mono-fucntional compounds by the CD exciton chirality method. Less

(1). 手性邻苯二甲酰胺，可用于对映异构体拆分和 X 射线晶体学测定醇的绝对立体化学。(2). CD 方法测定无环二醇的绝对立体化学。无环1,2-二苯甲酸酯体系的CD激子手性方法。(3)。 CD 激子手性方法和空间位阻 α-乙二醇的酯交换反应：毛喉素案例。(4)。环丁基甲醇的脂肪酶催化动力学拆分和 X 射线分析的绝对立体化学测定。(5)。 3,3'-二乙酰基-4,4'的立体化学， 6,6'-四甲氧基-2,2'-联苯二酚。(6). 天然双黄酮阻转异构体的全合成和绝对立体化学，[CD(+)362.0]-(-)4', 4''', 7, 7"-四-O-甲基铜黄酮。(7).CD激子手性方法在手性分析中的应用1,2-二胺。C2v-对称 2,3-萘二甲酰亚胺发色团的使用…更多。(8). 2-(l-萘基)丙烷-l, 2-二醇和相关化合物的对映体拆分和绝对立体化学。应用手性邻苯二甲酰胺进行对映体拆分2-(1-萘基)丙烷-1, 2-二醇，得到对映体纯(-)-二醇，其S绝对构型通过其(+)-对溴苯甲酸酯的X射线晶体学明确确定。 -2-甲氧基-2-(1-萘基)丙酸和相关化合物也通过化学关联法测定(S)-(-)-二醇。(9). CD激子手性方法测定单官能化合物绝对立体化学的新策略 CD激子手性方法已广泛应用于各种天然产物和手性合成化合物。以非经验方式确定它们的绝对构型然而，CD激子手性方法的应用仅限于具有两个或多个官能团的手性化合物。激子 CD 棉花效应只能在两个或多个发色团之间的相互作用中观察到，这是 CD 激子手性方法的一个弱点，因此它从未应用于单功能手性化合物。通过 CD 激子手性方法测定单功能化合物的绝对构型。