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).手性邻苯二甲酰胺，一种手性助剂，可用于对映异构体拆分和醇绝对立体化学的 X 射线晶体学测定。(2)。用于测定无环二醇的绝对立体化学的 CD 方法。 2. CD激子手性方法在无环1,2-二苯甲酸酯体系中的应用。(3)． CD 激子手性方法和空间位阻 α-乙二醇的酯交换苯甲酰化：Forskolin 案例。(4)。脂肪酶催化环丁基甲醇的动力学拆分和通过 X 射线分析测定绝对立体化学。(5)。 3,3'-二乙酰基-4,4', 6,6'-四甲氧基-2,2'-联苯二酚的对映拆分和绝对立体化学。(6)。双黄酮天然阻转异构体 [CD(+)362.0]-(-)4', 4''', 7,7"-四-O-甲基铜黄酮的全合成和绝对立体化学。(7). CD 激子手性方法在手性 1,2-二胺中的应用。C2v 对称的使用 2,3-萘二甲酰亚胺发色团...更多.(8)。 2-(1-萘基)丙烷-1, 2-二醇及相关化合物的对映拆分和绝对立体化学。应用手性邻苯二甲酰胺的方法对2-(l-萘基)丙烷-l,2-二醇进行对映拆分，得到对映体纯(-)-二醇，S 其绝对构型通过其(-)-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)丙酸和相关化合物的S绝对构型也通过与(S)-(-)-二醇的化学相关性确定。(9)。测定单官能化合物绝对立体化学的新策略 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。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，因为激子CD Cotton效应只能在两个或多个发色团之间的相互作用中观察到。这一直是一个弱 CD激子手性方法的重点，因此它从未应用于单官能手性化合物。我们报道了一种通过圆二色激子手性方法确定单功能化合物绝对构型的新策略。少

项目成果

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)-(

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。”

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: "Synthesis and Absolute Stereochemistry of(+)-Adociaquinones A and B" Tetrahedron:Asymmetry. 6. 375-376 (1995)

N.Harada：“( )-Adociaquinones A 和 B 的合成和绝对立体化学”四面体：不对称性。