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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07408032/
• 关键词: CD Exciton Method; Enantioresolution; Absolute Configuration; X-ray Crystallographic Analysis; Split Cotton Effects; Biflavone; CD Auxiliary; Conformational Analysis; CDスペクトル; 1,1-ビフェナンスリル; 絶対立体化学; 不斉補助基; キラルジクロロフタル酸法; 単一官能基化合物; 励起子相互作用; 円二

(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）。手性邻苯二甲酸酰胺，一种用于对映异构体分辨率和X射线晶体学的手性辅助，对醇的绝对立体化学测定。（2）。确定无环糖的绝对立体化学的CD方法。 2。将CD激子手性方法应用于无环1,2-二苯甲酸盐系统。（3）。 CD激子手性方法和通过跨酯化的立体阻碍的α-聚糖的苯甲酰化：Forskolin案例。（4）。通过X射线分析（5），脂肪酶催化的动力学分辨率以及确定绝对立体化学的动力学。 3,3'-diacetyi-4,4'，6,6'-四甲氧基-2,2'-2,2'-Biphenyldiol。（6）的映体解决和绝对立体化学。（6）。 Biflavone的天然肌异构体的总合成和绝对立体化学，[CD（+）362.0] - （ - ）4'，4'，4'，4''，7,7“ - tetra-o-tetra-o-methylCupressususflavone。（7）。 2,3-萘式辅助性发色团…（8）。（8）。它的绝对配置是通过其（ - ） - b-溴苯甲酸盐的X射线晶体学明确确定的。通过CD激子手性方法，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，以非经验方式确定其绝对构型。但是，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，因为激子CD棉花效应仅对于两个或多个发色团之间的相互作用才能观察到。这一直是CD Interigon Mathilation方法的弱点，因此它从未应用于单功能性手性化合物。我们报告了一种新的策略，该策略是通过CD Inveedon手性方法确定单核化合物的绝对构型。较少的

项目成果

T.-S.Kam, N.Harada: "Tenuisines A-C and Tenuiphylline,Novel Bisindoles from Kopsia Tenuis." Tetrahedron. 53. 12661-12670 (1997)

T.-S.Kam, N.Harada：“Tenuisines A-C 和 Tenuiphylline，来自 Kopsia Tenuis 的新型双吲哚。”

H.-Y.Li, N.Harada: "Total Synthesis and Absolute Stereochemistry of Natural Atropisomer of Biflavone, [CD(+)362.0]-(-)-4', 4''', 7, 7''-Tetra-O-methylcupressuflavone." J.Org.Chem.62. 7222-7227 (1997)

H.-Y.Li, N.Harada：“双黄酮天然阻转异构体的全合成和绝对立体化学，[CD( )362.0]-(-)-4, 4, 7, 7-Tetra-

N.Koumura, N.Harada: "X-Ray Crystallographic Determination of the Stereochemistry of a Unique Chiral Olefin, [CD(-)238.0]-(3R, 3'R)-(P, P)-(Z)-(+)-1, 1', 2, 2', 3, 3', 4, 4'-Octahydro-3, 3'-dimethyl-4, 4'-biphenanthrylidene." Enantiomer. 3. 251-253 (1998)

N.Koumura、N.Harada：“独特手性烯烃立体化学的 X 射线晶体测定，[CD(-)238.0]-(3R, 3R)-(P, P)-(Z)-(

N. Harada(Y. Mimaki): "A New Furostanol Saponin with Six Sugars from the Bulds of Allium sphaerosephalon Structural Elucidation by Modern NMR Techniques." Chemistry Letters. 431-432 (1996)

N. Harada(Y. Mimaki)：“通过现代核磁共振技术从球葱球茎中提取出含有六种糖的新型呋甾烷皂苷。”

N.Harada: "The Recent Advances in the Spectroscopy of Circular Dichroism (CD) and Its Application for Chiral Organic Compounds" Zhurn.Org.Khim.32. 167-179 (1996)

N.Harada：“圆二色性 (CD) 光谱及其在手性有机化合物中的应用的最新进展”Zhurn.Org.Khim.32。