1997 Fiscal Year Annual Research Report

円二色性スペクトル法の理論的展開と生物有機科学への応用

Research Project

Project/Area Number	07408032
Research Institution	Tohoku University
Principal Investigator	原田宣之東北大学, 反応化学研究所, 教授 (30006324)
Co-Investigator(Kenkyū-buntansha)	吉田彰宏東北大学, 反応化学研究所, 助手 (10292301)
Keywords	円二色性スペクトル / 励起子キラリティー法 / 絶対立体化学 / ねじれたパイ電子共役系 / キラルジクロロフタル酸法 / 新規不斉補助基 / シガトキシン / 天然アトロープ異性体
Research Abstract	有機化合物の絶対立体化学を非経験的に決定する方法として、単結晶X線解析法とならんで円二色性(CD)スペクトル法が有用である。我々は「CD励起子キラリティー法」および「ねじれたパイ電子共役系」の方法を開発確立し、多くの天然物や理論的に興味ある合成有機化合物に適用して、その絶対構造決定に成功してきた。本年度は次の研究成果をあげることができた。 1.立体障害の非常に大きい生理活性物質フォルスコリンにCD励起子キラリティー法を適用するための反応を見いだし、その絶対構造を確認できた。 2.アルコール類の光学分割とX線結晶解析による絶対配置決定に有用な新規不斉補助基としてキラルジクロロフタル酸を開発し、種々のアルコール系に適用し、光学分割と絶対配置の決定に成功した。 3.酵素リパーゼを用いて速度論的光学分割したシクロブチルメタノール誘導体に対して、上記の新規不斉補助基を応用し、絶対配置の決定に成功した。 4.超活性微量海産天然物であるシガトキシンの側鎖および骨格部分に対して、CD励起子キラリティー法を適用して、シガトキシン全体の絶対配置決定に成功した。 5.光学活性天然物の全合成に有用なビフェニル化合物の光学分割とX線結晶解析による絶対立体化学の決定に成功した。 6.3個の発色団を持つ励起子系のCDスペクトルに対して、理論計算を行い、実測と良く一致することを確認した。これにより、「CD励起子キラリティー法」の3発色団系への適用性を確立できた。 7.先にCDスペクトルの理論計算により絶対立体化学を理論的に決定していた天然アトロープ異性体ビフラボンの初めてのキラル全合成に成功し、その絶対構造を実験的に決定した。これにより理論計算結果の正しいことを証明できた。 8.光学活性体の合成の困難なジアリールメタノール類の光学分割と絶対配置の決定に成功した。

Research Products
(21 results)

All Other

All Publications (21 results)

[Publications] T.Sugioka, N.Harada,: "The CD Exciton Chirality Method and Benzoylation of Sterically Hindered α-Glycol by Trans-Esterification : Forskolin Case." Enantiomer. 2. 117-121 (1997)
[Publications] N.Harada: "Synthesis,Circular Dichroism,and Absolute Stereoshemistry of 1,1′: 4′,1″-Ternaphthalene Compounds." Chirality. 9. 623-625 (1997)
[Publications] N.Harada: "Absolute Configuration and Conformation of 1,1′: 4′,1″-Ternaphthalene Compounds as Determined by X-Ray Crystallography." Enantiomer. 2. 123-126 (1997)
[Publications] N.Harada: "Chiral Dichlorophthalic Acid Amide,an Improved Chiral Auxiliary Useful for Enantioresolution and X-Ray Crystallographic Determination of Absolute Sterochemistry." Enantiomer. 2. 303-309 (1997)
[Publications] 原田宣之: "旋光度" 化学. 52. 48-49 (1997)
[Publications] H.Nemoto, N.Harada: "Lipase-Catalyzed Kinetic Resolution of Cyclobutylmethanols and Determination of Absolute Stereochemistry by X-Ray Analysis." Enantiomer. 2. 127-131 (1997)
[Publications] H.-y.Li, N.Harada: "Isolation and NMR Studies of Di-D-fructose Anhydride III from Lycoris radiata Herbert by Supercritical Extraction." Carbohydrate Research. 299. 301-305 (1997)
[Publications] N.Harada: "HMR^<13>C Satellite Signals Useful for the First-Order Analysis of Complex Spin Systems." Enantiomer. 2(in press). (1997)
[Publications] H.Oguri, N.Harada: "Synthetic Study of Ciguatoxin. Absolute Configuration of the C2 Hydroxy Group." Tetrahedron. 53. 3057-3072 (1997)
[Publications] N.Harada: "Chemisty of Unique Chiral Olefins.1.Synthesis,Enantioresolution,Circular Dichroism,and Theoretical Determination of the Absolute Stereochemistry of trans-and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7241-7248 (1997)
[Publications] N.Harada: "Chemistry of Unique Chiral Olefins.2.Unexpected Thermal Racemization of cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7249-7255 (1997)
[Publications] N.Harada: "Chemistry of Unique Chiral Olefins.3.Synthesis and Absolute Stereochemistry of trans-and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7256-7264 (1997)
[Publications] M.Kuroda, N.Harada: "Novel Cholestane Glycosides from the Bulbs of Ornithogalum saundersiae and Their Cytostatic Activity on Leukemin HL-60 and MOLT-4 Cells." Tetrahedron. 53. 11549-11562 (1997)
[Publications] N.Harada: "Enantioresolution and Absolute Stereochemistry of 3,3′-Diacetyl-4,4′,6,6′-tetramethoxy-2,2′-biphenyldiol." Enantiomer. 2(in press). (1997)
[Publications] T.-S.Kam, N.Harada: "Tenuisines A-C and Tenuiphylline,Novel Bisindoles from Kopsia Tenuis." Tetrahedron. 53. 12661-12670 (1997)
[Publications] M.Watanabe, N.Harada: "A Convenient Synthesis of(1S,5S)-4-Alkyl-3-carbomethoxy-6,6-dimethylbicyclo[3.1.1]-hept-3-en-2-ones with Highly Optical Purity." J.Org.Chem.62. 2992-2995 (1997)
[Publications] J.-G.Dong, N.Harada: "Theoretical Calculation of Circular Dichroic Exciton-Split Spectra in Presence of Three Interactiong 2-Naphthoate Chromophores." Enantiomer. 2(in press). (1997)
[Publications] 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)
[Publications] N.Harada: "Enantioresolution and Absolute Stereochemistry of Diarylmethanols." Enantiomer. 2(in press). (1997)
[Publications] N.Harada: "Molecular Chirality by Isotopic Substitution.Synthesis,Absolute Configuration,and CD Spectra of Chiral Diphenylmethanols." Enantiomer. 2(in press). (1997)
[Publications] M.Satake, N.Harada: "The Absolute Configuration of Ciguatoxin." J.Am.Chem.Soc.119. 11325-11326 (1997)

1997 Fiscal Year Annual Research Report

円二色性スペクトル法の理論的展開と生物有機科学への応用

Principal Investigator

原田 宣之 東北大学, 反応化学研究所, 教授 (30006324)

Research Products

[Publications] T.Sugioka, N.Harada,: "The CD Exciton Chirality Method and Benzoylation of Sterically Hindered α-Glycol by Trans-Esterification : Forskolin Case." Enantiomer. 2. 117-121 (1997)

[Publications] N.Harada: "Synthesis,Circular Dichroism,and Absolute Stereoshemistry of 1,1′: 4′,1″-Ternaphthalene Compounds." Chirality. 9. 623-625 (1997)

[Publications] N.Harada: "Absolute Configuration and Conformation of 1,1′: 4′,1″-Ternaphthalene Compounds as Determined by X-Ray Crystallography." Enantiomer. 2. 123-126 (1997)

[Publications] N.Harada: "Chiral Dichlorophthalic Acid Amide,an Improved Chiral Auxiliary Useful for Enantioresolution and X-Ray Crystallographic Determination of Absolute Sterochemistry." Enantiomer. 2. 303-309 (1997)

[Publications] 原田宣之: "旋光度" 化学. 52. 48-49 (1997)

[Publications] H.Nemoto, N.Harada: "Lipase-Catalyzed Kinetic Resolution of Cyclobutylmethanols and Determination of Absolute Stereochemistry by X-Ray Analysis." Enantiomer. 2. 127-131 (1997)

[Publications] H.-y.Li, N.Harada: "Isolation and NMR Studies of Di-D-fructose Anhydride III from Lycoris radiata Herbert by Supercritical Extraction." Carbohydrate Research. 299. 301-305 (1997)

[Publications] N.Harada: "HMR^<13>C Satellite Signals Useful for the First-Order Analysis of Complex Spin Systems." Enantiomer. 2(in press). (1997)

[Publications] H.Oguri, N.Harada: "Synthetic Study of Ciguatoxin. Absolute Configuration of the C2 Hydroxy Group." Tetrahedron. 53. 3057-3072 (1997)

[Publications] N.Harada: "Chemisty of Unique Chiral Olefins.1.Synthesis,Enantioresolution,Circular Dichroism,and Theoretical Determination of the Absolute Stereochemistry of trans-and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7241-7248 (1997)

[Publications] N.Harada: "Chemistry of Unique Chiral Olefins.2.Unexpected Thermal Racemization of cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7249-7255 (1997)

[Publications] N.Harada: "Chemistry of Unique Chiral Olefins.3.Synthesis and Absolute Stereochemistry of trans-and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes." J.Am.Chem.Soc.119. 7256-7264 (1997)

[Publications] M.Kuroda, N.Harada: "Novel Cholestane Glycosides from the Bulbs of Ornithogalum saundersiae and Their Cytostatic Activity on Leukemin HL-60 and MOLT-4 Cells." Tetrahedron. 53. 11549-11562 (1997)

[Publications] N.Harada: "Enantioresolution and Absolute Stereochemistry of 3,3′-Diacetyl-4,4′,6,6′-tetramethoxy-2,2′-biphenyldiol." Enantiomer. 2(in press). (1997)

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

[Publications] M.Watanabe, N.Harada: "A Convenient Synthesis of(1S,5S)-4-Alkyl-3-carbomethoxy-6,6-dimethylbicyclo[3.1.1]-hept-3-en-2-ones with Highly Optical Purity." J.Org.Chem.62. 2992-2995 (1997)

[Publications] J.-G.Dong, N.Harada: "Theoretical Calculation of Circular Dichroic Exciton-Split Spectra in Presence of Three Interactiong 2-Naphthoate Chromophores." Enantiomer. 2(in press). (1997)

[Publications] 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)

[Publications] N.Harada: "Enantioresolution and Absolute Stereochemistry of Diarylmethanols." Enantiomer. 2(in press). (1997)

[Publications] N.Harada: "Molecular Chirality by Isotopic Substitution.Synthesis,Absolute Configuration,and CD Spectra of Chiral Diphenylmethanols." Enantiomer. 2(in press). (1997)

[Publications] M.Satake, N.Harada: "The Absolute Configuration of Ciguatoxin." J.Am.Chem.Soc.119. 11325-11326 (1997)

原田宣之東北大学, 反応化学研究所, 教授 (30006324)