Catalytic Control of Diels-Alder Reaction via Photoinduced Electron Transfer

通过光诱导电子转移催化控制狄尔斯-阿尔德反应

• 批准号: 09450318
• 负责人: FUKUZUMI Shunichi
• 金额: $ 8.83万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450318/
• 关键词: Catalysis; Potoinduced Electron Transfer; Diels-Alder Reaction; Scandium Ion; Redox Reaction; Excited State; 光Diels-Alder反応; 電子移動; 位置選択性の制御; アントラセン類; ビニルケトン類; 反応機構; 光電子移動; 触媒; 反応制御; 還化付加反応; 炭素-炭素結合生成; 位置異性体

Photochemical reactions involving photo-excited states can also be catalyzed as well as the thermal reactions of ground states. However, the lifetimes of excited sates are usually very short and accordingly any reaction of the excited state should be fast enough to compete the decay of the excited state to the ground state. Thus, there seems to be little chance of a catalyst to accelerate further the reactions of excited states, which are already fast. The reactivity of photoinduced electron transfer is automatically determined F once the pair of electron donor and acceptor, one of which is an excited state, is fixed. The excited state may have an energetically favorable electron transfer pathway with a substrate, otherwise the reaction would have no chance to compete with fast physical decay to the ground state (typically the lifetime is 10^<-6> to 10^<-12> s). Despite these apparent difficulties, we have developed a number of examples of photochemical reactions including Diels-Alder reactions that involve catalyzed electron transfer processes as the rate-determining steps. Fundamental concepts for catalysis of photoinduced electron transfer reactions have been established and photochemical redox reactions which would. otherwise be unlikely to occur are made possible to proceed efficiently by applying the catalysis on the photoinduced electron transfer steps.

涉及光激发态的光化学反应以及基态的热反应也可以被催化。然而，激发态的寿命通常非常短，因此激发态的任何反应都应该足够快以竞争激发态到基态的衰变。因此，催化剂似乎不太可能进一步加速已经很快的激发态反应。一旦电子供体和受体对（其中之一为激发态）固定，光诱导电子转移的反应性就会自动确定 F。激发态可能与底物具有能量上有利的电子转移路径，否则反应将没有机会与快速物理衰变竞争到基态（通常寿命为 10^<-6> 到 10^<-12> s）。尽管存在这些明显的困难，我们还是开发了许多光化学反应的例子，包括涉及催化电子转移过程作为速率决定步骤的狄尔斯-阿尔德反应。已经建立了光诱导电子转移反应催化的基本概念以及光化学氧化还原反应。通过在光诱导电子转移步骤上应用催化作用，使得原本不太可能发生的情况能够有效地进行。

项目成果

Shunichi Fukuzumi et al.: "Synthesis and Spectroscopic and Electrochemical Characterization of Di-and Tetrasubstituted C_<60> Derivatives" J.Phys.Chem.A. 102・22. 3898-3906 (1998)

Shunichi Fukuzumi 等：“二取代和四取代 C_<60> 衍生物的合成、光谱和电化学表征”J.Phys.Chem.A. 102·22 (1998)。

Shunichi Fukuzumi et al.: "Electron Transfer Kinetics for Generation of Organoiron(IV)Porphyrins and the Iron(IV)Porphyrin π Radical Cations" J.Am.Chem.Soc.121・4. 785-790 (1999)

Shunichi Fukuzumi 等人：“有机铁(IV)卟啉和铁(IV)卟啉π自由基阳离子生成的电子转移动力学”J.Am.Chem.Soc.121・4 (1999)。

Shunichi Fukuzumi et al.: "Formation of Radical Anion in the Reaction of p-Benzoquinone and C_<60> with Alkoxide Ions" J.Am.Chem.Soc.120・27. 6673-6680 (1998)

Shunichi Fukuzumi等人：“对苯醌和C_<60>与醇盐离子反应中自由基阴离子的形成”J.Am.Chem.Soc.120·27(1998)。

Shunichi Fukuzumi et al.: "Formation of C_<60> Adducts with Two Different Alkyl Groups via Combination of Electron Transfer and S_N2 Reactions" J.Am.Chem.Soc.121・36. 9220-9227 (1998)

Shunichi Fukuzumi 等：“通过电子转移和 S_N2 反应的组合形成 C_<60> 加合物与两个不同的烷基”J.Am.Chem.Soc.121・36 (1998)。

Shunichi Fukuzumi, Tomoyoshi Suenobu, Matthias Patz, Takeomi Hirasaka, Shinobu Itoh, Mamoru Fujitsuka, and Osamu Ito: "Selective One-Electron and Two-Electron Reduction of C_<60> with NADH and NAD Dimer Analogs via Photoinduced Electron Transfer" J.Am.Che

Shunichi Fukuzumi、Tomoyoshi Suenobu、Matthias Patz、Takeomi Hirasaka、Shinobu Itoh、Mamoru Fujitsuka 和 Osamu Ito：“通过光诱导电子转移用 NADH 和 NAD 二聚体类似物选择性地单电子和双电子还原 C_<60>” J.