有機軌道論-基礎有機化学における新概念の構築

1999 Fiscal Year Annual Research Report

• Project/Area Number: 09440215
• Research Institution: The University of Tokyo
• Principal Investigator: 友田 修司 東京大学, 大学院・総合文化研究科, 教授 (30092282)
• Co-Investigator(Kenkyū-buntansha): 岩岡 道夫 東京大学, 大学院・総合文化研究科, 助手 (30221097)
• Keywords: ジアステレオ選択性 / フロンティア軌道論

Research Abstract

昨年度に引き続き,以下の2つの研究テーマで研究をおこなった.
1.ジアステレオ面選択性の新煙識の構築
(a)1,3-Diselenan-5-one(1)のヒドリド還元の面選択性
新規化合物1の求核付加面選択性をエクステリアフロンティア軌道広がりモデル(EFOEModel)でeqattack優先と予測し,合成を行い,種々のヒドリド還元試薬と反応させ面選択性をNMRで決定したところ,EFOE Modelの予測と完全に一致した.
(b)含ヘテロ元素6員環ケトンのヒドリド還元の面選択性
4-Heteracyclohexanone(2)と3-Heteracyclohexanonee(3)(heteroatom=SorSe)の求核付加面選択性をEFOE Modelで2はax-attack,3はeq-attack優先と予測した.そこで,2と3をチオベンズアルデヒド(またはセレナベンズアルデヒド)とDanishefskyジエンのDiels-Alder反応で合成し,種々のヒドリド還元試薬と反応させ面選択性をNMRで決定したところ,EFOE Modelの予測と完全に一致した.これらの実験結果は,いずれもEFOE Modelのジアステレオ面選択性予測理論としての有用性を示すものである.
2.微弱相互作用系の定量解析
(a)Br…SePhBr系の微弱相互作用作用定量評価と反応経路解析
PhSeBrとBr anionの固相における相互作用エネルギーをX線データベース解析とab initio MO計算と組み合わせて定量評価することに成功した.
(b)F…SePhX(X=CN,Me,SePh,SPh,Cl、Br)の溶液相における微弱相互作用定量評価に,NMRのスピン結合の温度変化のsimulation fitting法により成功した.

Research Products

• [Publications] S. Tomoda: "The exterior frontier orbital extension model"Chem. Rev.. 99・5. 1243-1263 (1999)
• [Publications] S. Tomoda: "Natural bond orbital analysis of hyperconjugative stabilization effects in the transition states of cyclohexanone reduction with lithium tetrahydridoaluminate"Chem. Comm.. 1999. 423-424 (1999)
• [Publications] S. Tomoda: "Origin of π-Facial Stereoselectivity of Nucleophilic Addition to Carbonyl Compounds. Application of the Exterior Frontier Orbital Extension Model"Tetrahedron. 55. 3871-3882 (1999)
• [Publications] S. Tomoda: "Quantitative Evaluation of Steric Effect for π-Facial Stereoselection. π-Plane-Divided Accessible Space"Chem. Commun.. 1999. 621-622 (1999)
• [Publications] S. Tomoda: "Origin of π-Facial Stereoselectivity in Nucleophilic Additions. Application of the Exterior Frontier Orbital Extension Model to Imines and Iminium Ions"J. Org. Chem.. 64. 5396-5400 (1999)
• [Publications] S. Tomoda: "Origin of π-Facial Stereoselection in Nucleophilic Additions of Adamantanones. A New Interpretation Based on the Exterior Frontier Orbital Extension Model"Tetrahedron. 55. 5303-5318 (1999)
• [Publications] S. Tomoda: "Origin of π-Facial Stereoselectivity in Nucleophilic Addition. Application of the Exterior Frontier Orbital Extensron Model to Substituted Bicyclo[2.2.1]heptan-7-Ones"Chem. Lett.. 1999. 353-354 (1999)
• [Publications] S. Tomoda: "Origin of π-Ficial Diastereoselection in Hydride Reduction of Piperidones. The Importance of Ground-State Effects."Chem. Lett.. 1999. 625-626 (1999)
• [Publications] S. Tomoda: "Origin of π-Facial Stereoselection in Nucleophilic Addition to 1,3-Diheteran- 5-ones (Heteroatom = O or S). Theoretical Evidence for the Importance of Ground-State Effects"Chem. Lett.. 1999. 1115-1116 (1999)
• [Publications] S. Tomoda: "Intramolecular non-bonded interaction between selenium and oxygen as revealed by O-17 and Se-77 NMR spectroscopy and natural bond orbital analysis"Chem. Commun.. 1999. 205-206 (1999)
• [Publications] S. Tomoda: "Structure and natural bond orbital analysis of oxiranes substituted with a group 14 element. A comment on SN2 reactivrty"Chem. Lett.. 1999. 409-410 (1999)
• [Publications] S. Tomoda: "Origin of π-facial diastereoselection in carbonyl addition. Applicatron of the exterior frontier orbital extension model to 1,3-diheteran-5-ones (heteroatom = O,S)"Heterocycles. (印刷中). (2000)
• [Publications] 共同執筆(野依良治他偏): "大学院有機化学"東京化学同人. 480 (1999)
• [Publications] S.Tomoda (共同執筆): "Organoselenium Chemistry"Springer-Verlag. 260 (1999)