1999 Fiscal Year Annual Research Report

CD励起子法の新しい展開:単一官能基をもつ天然有機化合物への新規応用戦略

Research Project

Project/Area Number	11480159
Research Category	Grant-in-Aid for Scientific Research (B)
Research Institution	Tohoku University
Principal Investigator	原田宣之東北大学, 反応化学研究所, 教授 (30006324)
Keywords	CD励起子カイラリティー法 / キラルモノアルコール / CD補助基 / 励起子分裂型CD / 分子力場計算 / 分子軌道法 / 配座解析 / 絶対配置
Research Abstract	有機化合物の絶対構造を非経験的に決定する方法として、「円二色性励起子カイラリティー法」が有用である。この方法の欠点は、発色団間の相互作用を使用するため、適用が複数の官能基を持つ系に限られ、monoalcoholなど単一の官能基を持つ系に適用できないことであった。我々は今回、全く新しい概念と戦略に基づいて、単一の官能基を持つ系の絶対立体化学を「CD励起子カイラリティー法」で決定する研究を開始し、以下の研究成果を得た。 1.CD補助基として、2個の(1-Naphthyl)基をもつ一般的なアキラルな系を採用した:i)230nm付近にCD励起子法に好都合な非常に強く、長軸方向に偏光したUV吸収帯がある。ii)このCD補助基を単一官能基をもつキラル分子にエステル結合あるいはエーテル結合で結合させる。iii)キラル分子のキラリティーが伝播し、CD補助基の2個のナフタレン発色団はねじれたキラルな立体配座を取る。iv)ねじれに対応して、励起子カイラリティーが生じ、励起子分裂型Cotton効果が観測される。v)分子力場計算あるいは分子軌道法を駆使して配座解析を行い、発色団間の励起子カイラリティーと元の分子の絶対配置を理論的に結び付ける。vi)配座解析の結果と実測のCDを比較し、絶対配置を決定できた。 2.di(1-naphthyl)acetic acidを合成し、キラルなモノアルコールと縮合させてエステル体を合成した。このエステル体のCDを測定して、実際にどのような励起子分裂型Cotton効果が観測されるかを検証した。特に種々の第2級アルコール系では非常に強い励起子CDが得られ、立体配座の理論計算と組み合わせて絶対配置を明確に決定できる事を明らかにした。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] R.W.J.Zijlstra,N.Harada: "Chemistry of Unique chiral Olefins. Part 4.Theoretical Studies of the Racemization Mechanism of trans-and cis-1,1',2,2',3,3',4,4'-Octahydro-4,4'-biphenanthrylidenes"Journal of Organic Chemistry. 64. 1667-1674 (1999)
[Publications] S.kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of 2-(1-Naphthyl) propane-1,2-diol and Related Compounds"Enantiomer. 4. 141-145 (1999)
[Publications] M.Watanabe,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method: Absolute Configurations of (2-Methylphenyl) phenylmethanol and Related Compounds"Tetrahedron: Asymmetry. 10. 2075-2078 (1999)
[Publications] N.Koumura,N.Harada: "Light-driven Monodirectional Molecular Rotor"Nature. 401. 152-155 (1999)
[Publications] A.Ichikawa,N.Harada: "Absolute Stereochemistry of 2-Hydroxy-2-(1-naphthyl) propionic Acid as Determined by the H^1 NMR Anisotropy Method"Tetrahedron: Asymmetry. 10. 4075-4078 (1999)
[Publications] K.Ogura,N.Harada: "Novel Appearance of Chirality in a 2,5-Di(p-tolyl) thiophene π-System by the Aid of a Remote Chiral Carboxyl Group"Tetrahedron Letters. 40. 9065-9068 (1999)
[Publications] S.Kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylmethanols"Enantiomer. 5(in press). (2000)
[Publications] N.koumura,N.Harada: "Synthesis, Circular Dichroism, and Absolute Stereochemistry of 1,1',2,2',3,3',4,4'-Octahydro-3,3'-dimethyl-4,4'-biphenanthryl"Enantiomer. 5(in press). (2000)
[Publications] T.Nehira,N.Harada: "Circular Dichroism and Absolute Stereochemistry of [8]Paracyclophane-10-carbonitrile and Related Compounds"Enantiomer. 5(in press). (2000)
[Publications] S.Murai,N.Harada: "Synthesis, Circular Dichroism,and Absolute Stereochemistry of a Fecht Acid Analog and Related Compounds"Enantiomer. 5(in press). (2000)
[Publications] V.Petrov,N.Harada: "Step By Step Filter based program for calculations of highly informative derivative curves"Computor in Chemistry. (in press). (2000)
[Publications] M.Kosaka,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method:Absolute Configurations of Substituted Benzylic Alcohols"Chirality. 12(in press). (2000)
[Publications] N.Harada: "2-Methoxy-2-(1-naphthyl) propionic Acid, a Powerful Chiral Auxiliary for Enantioresolution of Alcohols and Determination of Their Absolute Configurations by the H^1 NMR Anisotropy Method"Tetrahedron: Asymmetry. 11(in press). (2000)
[Publications] 原田宣之: "化学「コットン効果」"化学同人. 3 (1999)
[Publications] 原田宣之(分担): "エッセンシャル化学辞典"東京化学同人. 684 (1999)
[Publications] N.Harada: "The Biology-Chemistry Interface, 'Circular Dichroism Spectroscopy and Absolute Stereochemistry of Biologically Active Compounds'"Marcel Dekker, Inc.. 52 (1999)

1999 Fiscal Year Annual Research Report

CD励起子法の新しい展開:単一官能基をもつ天然有機化合物への新規応用戦略

Principal Investigator

原田 宣之 東北大学, 反応化学研究所, 教授 (30006324)

Research Products

[Publications] R.W.J.Zijlstra,N.Harada: "Chemistry of Unique chiral Olefins. Part 4.Theoretical Studies of the Racemization Mechanism of trans-and cis-1,1',2,2',3,3',4,4'-Octahydro-4,4'-biphenanthrylidenes"Journal of Organic Chemistry. 64. 1667-1674 (1999)

[Publications] S.kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of 2-(1-Naphthyl) propane-1,2-diol and Related Compounds"Enantiomer. 4. 141-145 (1999)

[Publications] M.Watanabe,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method: Absolute Configurations of (2-Methylphenyl) phenylmethanol and Related Compounds"Tetrahedron: Asymmetry. 10. 2075-2078 (1999)

[Publications] N.Koumura,N.Harada: "Light-driven Monodirectional Molecular Rotor"Nature. 401. 152-155 (1999)

[Publications] A.Ichikawa,N.Harada: "Absolute Stereochemistry of 2-Hydroxy-2-(1-naphthyl) propionic Acid as Determined by the H^1 NMR Anisotropy Method"Tetrahedron: Asymmetry. 10. 4075-4078 (1999)

[Publications] K.Ogura,N.Harada: "Novel Appearance of Chirality in a 2,5-Di(p-tolyl) thiophene π-System by the Aid of a Remote Chiral Carboxyl Group"Tetrahedron Letters. 40. 9065-9068 (1999)

[Publications] S.Kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylmethanols"Enantiomer. 5(in press). (2000)

[Publications] N.koumura,N.Harada: "Synthesis, Circular Dichroism, and Absolute Stereochemistry of 1,1',2,2',3,3',4,4'-Octahydro-3,3'-dimethyl-4,4'-biphenanthryl"Enantiomer. 5(in press). (2000)

[Publications] T.Nehira,N.Harada: "Circular Dichroism and Absolute Stereochemistry of [8]Paracyclophane-10-carbonitrile and Related Compounds"Enantiomer. 5(in press). (2000)

[Publications] S.Murai,N.Harada: "Synthesis, Circular Dichroism,and Absolute Stereochemistry of a Fecht Acid Analog and Related Compounds"Enantiomer. 5(in press). (2000)

[Publications] V.Petrov,N.Harada: "Step By Step Filter based program for calculations of highly informative derivative curves"Computor in Chemistry. (in press). (2000)

[Publications] M.Kosaka,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method:Absolute Configurations of Substituted Benzylic Alcohols"Chirality. 12(in press). (2000)

[Publications] N.Harada: "2-Methoxy-2-(1-naphthyl) propionic Acid, a Powerful Chiral Auxiliary for Enantioresolution of Alcohols and Determination of Their Absolute Configurations by the H^1 NMR Anisotropy Method"Tetrahedron: Asymmetry. 11(in press). (2000)

[Publications] 原田宣之: "化学「コットン効果」"化学同人. 3 (1999)

[Publications] 原田宣之(分担): "エッセンシャル化学辞典"東京化学同人. 684 (1999)

[Publications] N.Harada: "The Biology-Chemistry Interface, 'Circular Dichroism Spectroscopy and Absolute Stereochemistry of Biologically Active Compounds'"Marcel Dekker, Inc.. 52 (1999)

原田宣之東北大学, 反応化学研究所, 教授 (30006324)