Electron Transfer Phenomena between Hetero Atoms and Their Characteristics and Applications

杂原子间的电子转移现象及其特点和应用

• 批准号: 63303009
• 负责人: TORII Sigeru
• 金额: $ 8.19万
• 依托单位: OKAYAMA University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63303009/
• 关键词: Electron transfer; Organometalic complex; Bimetal Redox System; Electroorganic Reactions; Photoelectron Transfer reaction; Metal Complex-catalyzed Reaction; Enantioselective Reaction; Chiral Catalyst; 光誘起電子移動反応

Electron transfer between different elements has been intensively investigated from mechanistic and synthetic view points. The present cooperative research covers (1) electron transfer in two and three component metal redox systems, (2) electron transfer between organometalic complexes and organic compounds, (3) photo- and electrochemically induced electron transfer reactions, and (4) their synthetic applications. In the first category, newly designed two and three components metal redox systems, e.g., Ti/Zn, Ni/Zn, Nb/Zn, Ta/Zn, Pb/Al, Ti/Al, and Ni/Pb/Al may provide potential electron transfer systems, each of which can promote the characteristic carbon-carbon bond making reactions. The electron transfer systems comprising transition metal complexes and organic compounds have opened unique entries to various highly selective functionalization of olefins and silyl compounds. Electron transfer reaction between enzyme complexes in biological system has been also investigated using porphyrin dimmer linked by polymethylene diamide bond as a model system. On the other hand, under the plioto- and electrochemical conditions, the combinations of metal and organic redoxes, e.g., heteroaromatic o-quinones/NADH, copper complex/allyl halides, phenanthrene/group 4B metal complexes, and copper(II) salts/vinyl bromides, have been found to work as an efficient electron transfer system. The above mentioned electron transfer reactions can be applied successfully to various synthetic purposes, particularly, to enantio- and diastereoselective carbon-carbon bond formation, e.g., asymmetric [2+2]cycloaddition, asymmetric glyoxylate-ene reaction, oxygenation and hydrosilylation of olefins, cyclization of eneynes and diynes, rotamer distribution controlled C=C face differentiation, chirafity transfer of L-valine to homoallylamines and others.

不同元素之间的电子转移已经从机械和合成的角度进行了深入的研究。目前的合作研究包括：(1)二组分和三组分金属氧化还原体系中的电子转移，(2)有机金属配合物与有机化合物之间的电子转移，(3)光和电化学诱导的电子转移反应，以及(4)它们的合成应用。在第一类中，新设计的二组分和三组分金属氧化还原体系，如Ti/Zn、Ni/Zn、Nb/Zn、Ta/Zn、Pb/Al、Ti/Al和Ni/Pb/Al可能提供潜在的电子转移体系，每一种体系都可以促进特征性的碳-碳成键反应。由过渡金属配合物和有机化合物组成的电子转移体系为烯烃和硅基化合物的各种高选择性功能化开辟了独特的途径。以卟啉二聚体为模型体系，研究了生物体系中酶配合物之间的电子转移反应。另一方面，在电化学条件下，金属和有机氧化还原的组合，如杂芳邻醌/NADH、铜配合物/烯丙基卤化物、菲/ 4B族金属配合物和铜（II）盐/乙烯基溴化物，已被发现作为一个有效的电子转移体系。上述电子转移反应可以成功地应用于各种合成目的，特别是对映和非对映选择性碳-碳键的形成，如不对称[2+2]环加成反应、不对称乙醛-烯反应、烯烃的氧合和硅氢化反应、烯炔和二炔的环化反应、旋转体分布控制的C=C面分化、l -缬氨酸向同丙烯胺的手性转移等。

项目成果

Kenji UNEYAMA: "Trifluoroacetimidoyl Chlorides as a New Trifluoromethyl Building Block for Fluorinated Nitrogen Heterocycles" Tetrahedron Lett.30. 4821-4824 (1989)

Kenji UNEYAMA：“三氟乙酰亚胺酰氯作为氟化氮杂环的新三氟甲基构件”Tetrahedron Lett.30。

Masao TOKUDA: "An Efficient Electrochemical Coupling of Allylic Halides by Using a Copper Anode" Chem.Lett.945-948 (1988)

Masao TOKUDA：“使用铜阳极实现烯丙基卤化物的高效电化学耦合”Chem.Lett.945-948 (1988)

Akira Yanagusawa: "Double Alkylation ofα,βーUnsaturated Acetals.An Inverse Polarity Approach" J.Am.Chem.Soc.111. 366-368 (1989)

Akira Yanagusawa：“α,β-不饱和缩醛的双烷基化。反极性方法”J.Am.Chem.Soc.111 (1989)。

Hideo Tanaka: "Electroreductive "Barbier Type" Allylation of Imines with a Combination of a Pb(0)/Pb(II) Redox Mediator and Sacrificial Anode(Al)" TETRAHEDRON LETT., 30, 4161-4164(1989).

Hideo Tanaka：“结合 Pb(0)/Pb(II) 氧化还原介体和牺牲阳极 (Al) 进行亚胺的电还原“巴比尔型”烯丙基化”TETRAHEDRON LETT., 30, 4161-4164(1989)。

Yoshihiko Ito: "Synthesis of Unsymmetrical Dialkynyl Imines. Stepwise Coupling of N-Phenyl Phenylthioimidoyl Chloride with Alkynyltin Compounds" CHEM.LETT., 1989, 1261-1264.

Yoshihiko Ito：“不对称二炔基亚胺的合成。N-苯基苯基硫代亚胺酰氯与炔基锡化合物的逐步偶联”CHEM.LETT.，1989，1261-1264。