SELECTIVITY AND REACTIVITY OF ORGANIC REACTIONS CONTROLLED BY THE COMBINED EFFECTS OF GROUND AND TRANSITION STATES

基态和过渡态联合效应控制的有机反应的选择性和反应性

• 批准号: 07304075
• 负责人: TAKEUCHI Ken'ichi
• 金额: $ 1.73万
• 依托单位: KYOTO 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 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07304075/
• 关键词: Ground State Structure; Transition State Structure; Selectivity and Reactivity; Reaction Intermediate; Carbocations; Carbenes; Organic Stereochemistry; Molecular Orbital Calculations

The group was devided into following three subgroups. The members whose names are shown in parentheses obtained successful results in the given research projects.Subgroup (1) for the study of structural factors controlling energies of ground and transition states : Steric control of nucleophilic solvent intervention in solvolysis (K.Takeuchi) ; Electronic structure of tetramethyleneethane (H.Iwamura) ; Stabilization of highly reactive species in novel reaction sites (R.Okazaki) ; Nucleophilic substitution and elimination of vinyl iodonium salts (T.Okuyama) ; Solute-solvent interaction in transition state (Y.Kondo) ; Isomerization via excited transition state of radicalcations of stilbene derivatives (H.Sakuragi) ; Reduction-oxidation behavior of benzyl radicals (Y.Sawaki) ; Kinetic stabilization of highly strained paracyclophanes (T.Tsuji).Subgroug (2) for the study of stereochemical characteristics of ground and transition state structures : Mechanism of sonochemical activation (T.And … More o) ; Orientation of polar group and stereoselectivity in hydride reduction (A.Ohno) ; Design of strained electron-transfer system (A.Oku) ; High enantio-selective reaction by use of enantiopure nickel catalysts (S.Kanemasa) ; Ground and transition state effects on the selectivity of hydride reduction (S.Tomoda) ; Steric effects in the reactions of alkylcarbenes (H.Tomioka) ; Analysis of steric pathways by use of OMEGA_S (M.Hirota) ; Theoretical prediction of reactivity by including transition state (H.Fujimoto) ; Isotope effect on reaction pathway of nucleophilic reactions to carbonyl group (H.Yamataka).Subgroup (3) for the study of characteristics of ground and transition state structures involving heteroatoms : Trap of intermediates of Berry pseudorotaion and kinetics of interconversion (K.Akiba) ; Rearrangement of 3,3'-bis (silacyclopropane) and bis (silacyclopropene) (W.Ando) ; Synthesis and properties of azacalixarenes (T.Inazu) ; Nucleophilic substitution of aromatic nitro compounds by use of nonionic strong bases (N.Ono) ; Mn-salen catalyzed asymmetric epoxidation (T.Katsuki) ; Role of heteroatoms in controlling nucleophilic substitution to unsaturated bonds (T.Kitamura) ; Mechanism of alcohol addition to silatriafulvenes (M.Kira) ; Nonclassical aromatic nitration (H.Suzuki) ; Structures and reactions of metallofullerenes (S.Nagase). Less

该组被分为以下三个亚组。括号中显示名称的成员在给定的研究项目中获得了成功的结果。（1）用于研究控制地面和过渡状态能量的结构因子：核植酸溶液干预溶液中的空间控制（K.Takeuchi）；四甲基乙烷（H.iwamura）的电子结构；在新型反应部位稳定高反应性物种（R. Okazaki）；亲核取代和消除乙烯基碘盐盐（T. Okuyama）；过渡状态（Y.Kondo）中的溶质 - 溶剂相互作用；通过激发Silbene衍生物辐射的激发过渡状态（H。Sakuragi）的异构化；苄基自由基的还原氧化行为（Y. Sawaki）；高度紧张的寄生虫（T. tsuji）的动力学稳定。用于研究地面和过渡状态结构的立体化学特征的subgroug（2）：超声激活的机制（T. t. and…更多O）；极性基团的方向和氢化物还原中的立体选择性（a.ohno）；应变电子转移系统（A.OKU）的设计；使用对映镍催化剂（S.Kanemasa）使用高对映射选择性反应；地面和过渡态对氢化物还原的选择性的影响（s.tomoda）；烷基碳烯反应的空间作用（H.Tomioka）；通过使用Omega_s（M.Hirota）分析空间途径；通过包括过渡状态（H.Fujimoto）对反应性的理论预测；同位素对核反应对羰基的反应途径（H. yamataka）.subgroup（3），用于研究涉及杂原子的地面和过渡状态结构的特征：浆果假核的陷阱和互连的动力学的中间体（K.Akiba）; 3,3'-双（硅烷丙烷）和双（硅丙丙丙泳）（W.Ando）的重排； Azacalixarenes（T.Inazu）的合成和特性；通过使用非离子强碱（N.Ono），芳香族硝基化合物的亲核取代； Mn-盐塞催化的不对称环氧化（T.Katsuki）；杂原子在控制不饱和键的核取代（T.Kitamura）中的作用；饮酒的机理添加了Silatriafulvenes（M.Kira）；非经典芳族硝化（H.Suzuki）；金属氟苯甲的结构和反应（S.nagase）。较少的

项目成果

稲津孝彦: "Efficient Synthesis of 2, 11, 20-Triaza [3. 3. 3] (2, 6) pyridinophane" J. Org. Chem.61. 8304-8306 (1996)

Takahiko Inazu：“2, 11, 20-Triaza [3. 3. 3] (2, 6) 吡啶芬的高效合成”J. Org. 8304-8306 (1996)。

KANEMASA,Shuji et al.: "Exclusively endo-Selective Lewis Acid-Catalyzed Hetero Diels-Alder Reactions of (E) -1-Phenylsulfonyl-3-alken-2-ones with Vinyl Ethers" Tetrahedron. Vol.52. 1205-1220 (1996)

KANEMASA、Shuji 等人：“(E) -1-苯基磺酰基-3-链烯-2-酮与乙烯基醚的独家内选择性路易斯酸催化杂狄尔斯-阿尔德反应”四面体。

TOMODA,Shuji et al.: "Nature of the Intramolecular Se...N Non-bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by H-1, C-13, Se-77, and N-15 NMR Spectroscopy" J.Am.Chem.Soc.Vol.118. 8077-8084 (1996)

TOMODA、Shuji 等人：“2-Selenobenzylamine 衍生物的分子内 Se...N 非键相互作用的性质。通过 H-1、C-13、Se-77 和 N-15 NMR 光谱进行实验评估”

OKAZAKI,Renji et al.: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde, (2,4,6-Tri-butyl) thiobenzaldehyde" Bull.Chem.Soc.Jpn.Vol.69. 719-724 (1996)

OKAZAKI，Renji 等人：“稳定硫代醛、(2,4,6-三丁基)硫代苯甲醛的环加成和氧化反应”Bull.Chem.Soc.Jpn.Vol.69。

安藤喬志: "Standardization of Ultrasonic Power for Sonochemical Reactions" Ultrasonics Sonochem. 3(印刷中). (1996)

Takashi Ando：“声化学反应的超声波功率标准化”Ultrasonics Sonochem 3（出版中）。