Electroorganic Synthesis Mediated by Metalloenzyme Models
金属酶模型介导的有机电合成
基本信息
- 批准号:09450333
- 负责人:
- 金额:$ 8.64万
- 依托单位:
- 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 1999
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
In this work, the carbon-skeleton rearrangements as mediated by hydrophobic vitamin B12 derivatives were investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides with various electron-withdrawing groups were carried out, and the electrochemical carbon-skeleton rearrangements proceeded effectively via formation of anionic intermediates. These reactions can be also applied to the ring-expansion reactions. We have carried out the electrolysis of an alkyl halide having two ester groups and one phenyl group on the β-carbon atom in the presence of a catalytic amount of the hydrophobic vitamin B12. The migration of the pheny group was observed under the conditions forming an radical intermediate. The ester-migrated product was detected under the conditions forming anionic intermediate. This is the first successful example in selecting a migrating group by electrolysis potential. We have also prepared a strapped hydrophobic vitamin B12 in order to change the enantioselectivity. The controlled-potential electrolysis of a racemic alkyl halide having phenyl, methoxy, and carboxylic ester groups on the same carbon atom were carried out. The simple hydrophobic vitamin B12 tends to bind S-enantiomers more favorably. On the other hand, strapped hydrophobic vitamin B12 acts to bind R-enantiomers more favorably. These results suggested that the stability of alkylated complexes was dominated the enantioselectivity of reduction products.We prepared bis-cobalt complex with salen-type ligand for the catalyst. When electrolysis of benzyl bromide was carried out at - 1.4 V vs. SCE in the presence of the bis-cobalt complex, major product was bibenzyl. This result suggests that the bis-cobalt complex will be an excellent catalyst for dimerization reactions.
在本工作中,我们在电化学条件下研究了疏水性维生素B12衍生物介导的碳骨架重排反应。对具有不同吸电子基团的卤代烷进行了控制电位电解,通过阴离子中间体的形成有效地进行了电化学碳骨架重排。这些反应也适用于扩环反应。在催化量的疏水维生素B12存在下,我们在β-碳原子上进行了具有两个酯基和一个苯基的卤代烷的电解。在形成自由基中间体的条件下,观察到苯基的迁移。在形成阴离子中间体的条件下检测到酯迁移产物。这是利用电解电势选择迁移基团的第一个成功例子。我们还制备了一种带疏水的维生素B12,以改变对映体选择性。对一个外消旋卤代烷基化合物进行了控制电位电解,该化合物具有苯基、甲氧基和羧酸酯基团。简单的疏水维生素B12倾向于更有利地结合S对映体。另一方面,捆绑的疏水维生素B12更有利于R-对映体的结合。这些结果表明,烷基化配合物的稳定性主要取决于还原产物的对映选择性。我们制备了Salen型配体的双钴配合物作为催化剂。在双钴络合物存在下,在-1.4V vs.SCE条件下电解溴化苄时,主要产物为联苯基。这一结果表明,双钴络合物将是一种优良的二聚反应催化剂。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Yoshio Hisaeda: "Novel Trends in Electroorganic Synthesis"Springer. 6 (1998)
Yoshio Hisaeda:“有机电合成的新趋势”施普林格。
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Y. Hisaeda, Y. Inoue, K. Asada, T. Nishioka: "Catalytic Activity of Vitamin B12 Derivative Having Amino Acid Residues"Novel Trends in Electroorganic Synthesis. 403-404 (1998)
Y. Hisaeda、Y. Inoue、K. Asada、T. Nishioka:“具有氨基酸残基的维生素 B12 衍生物的催化活性”有机电合成的新趋势。
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Y. Hisaeda: "Electrochemical Molecular Transformation mediated by Bio-related Cobalt Complexes"Proceedings of The 3rd CMC-Kyushu University Chemistry Symposium. 13-14 (1999)
Y. Hisaeda:“生物相关钴配合物介导的电化学分子转化”第三届CMC-九州大学化学研讨会论文集。
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Hisashi Shimakoshi: "Electron Paramagnetic Resonance Studies on Cobalt(II)Porphycene and Its Monomeric Oxygen Adduct" J.Inorg.Biochem.67. 123 (1997)
Hisashi Shimakoshi:“钴(II)卟啉及其单体氧加合物的电子顺磁共振研究”J.Inorg.Biochem.67。
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- 影响因子:0
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Y. Hisaeda, J. Takenaka, Y. Murakami: "Hydrophobic Vitamin B12. Part 14. Ring-expansion Reactions Catalyzed by Hydrophobic Vitamin B12 under Electrochemical Conditions in Nonaqueous Medium"Electrochemica Acta. 42. 2165-2172 (1997)
Y. Hisaeda、J. Takenaka、Y. Murakami:“疏水性维生素 B12。第 14 部分。非水介质中电化学条件下疏水性维生素 B12 催化的扩环反应”电化学学报。
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HISAEDA Yoshio其他文献
HISAEDA Yoshio的其他文献
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{{ truncateString('HISAEDA Yoshio', 18)}}的其他基金
Challenge for Construction of Metal Organic Frameworks with Photosensitizer and Application as New Solid Catalysts
光敏剂构建金属有机骨架及其作为新型固体催化剂的应用面临的挑战
- 批准号:
24655134 - 财政年份:2012
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
Challenge for Detoxification of Arsenic by Methylated Metal Complex
甲基化金属络合物解砷的挑战
- 批准号:
22655018 - 财政年份:2010
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
New Molecular Transformations Mediated by Bioinspired Catalysts
仿生催化剂介导的新分子转化
- 批准号:
21245016 - 财政年份:2009
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Organic/Inorganic Hybrid Catalysts with Metalloenzyme Functions
具有金属酶功能的有机/无机杂化催化剂
- 批准号:
18065018 - 财政年份:2006
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Dynamic Structure and Novel Functions of Dicobalt Complexes
二钴配合物的动态结构和新功能
- 批准号:
16350076 - 财政年份:2004
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of Novel Tetrapyrrole Ligands and Their Metal Complexes with New Functions
新型四吡咯配体及其新功能金属配合物的研制
- 批准号:
13440198 - 财政年份:2001
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Organic Synthesis Catalyzed by Cobalt Complexes with Co-C Bond
Co-C键钴配合物催化有机合成
- 批准号:
07651034 - 财政年份:1995
- 资助金额:
$ 8.64万 - 项目类别:
Grant-in-Aid for Scientific Research (C)