Electrogenerated Unusual Active-Species

1993-1995年开展了“电生成异常活性物种”的机理和合成研究。对以下五类反应进行了深入研究，其中重点放在活性物种的突出前体的设计以及在有机合成中的应用上，这些有机合成不能或不容易通过常规化学方法实现。1）有机金属化合物的电氧化和还原在电还原介质中产生的金属络合物的独特行为使我们能够实现几种新的金属氧化还原，用于碳-碳键形成和对映体选择性和/或特定官能化的诱导催化体系。2）杂原子化合物的电氧化和还原缺电子杂原子物质的电氧化生成和反应、高度配位的杂原子化合物的生成和硫化物的化学选择性官能化，这些通过常规化学反应不容易实现，4）生长放电电解（Grow Discharge Electrolysis）研究了辉光放电等离子体中的接触辉光放电电解和聚合反应，以产生用常规电化学方法很难形成的超活性物种。电生成活性物质的合成应用电生成活性物质在有机合成中的潜力已经通过合成有用的化学品和天然产物得到很好的证明，例如，雪松烷型倍半萜、（-）-雌甾烯等。

The research project in 1993-1995 on "electrogenerated unusual active-species" was carried out in both mechanistic and syntetic aspects. Following five categories of reactions were intensively investigated, wherein emphasis has been placed on design of prominent precursors of the active species as well as applications to organic syntheses which can not or not easily be achieved by conventional chemical methods.1) Electrooxidation and Reduction of Organometal CompoundsThe unique behavior of the metal complexes generated in electroreductive media allowed us to realize several new metal redox-induced catalytic systems for carbon-carbon bond making and enantio-selective and/or specific functionalization.2) Electrooxidation and Reduction of Hetero Atom CompoundsElectrooxicative generation and reactions of electron deficient hetero atom species, generation of highly coordinated hetero atom compounds, and chemoselective functionalization of sulfides, which are not easily achieved by conventional chemical reactions, have been developed.3) Enzymatic Electron Transfer SystemsSimulation of enzymatic catalysis and design of a highly efficient catalyst for organic synthesis were carried out.4) Grow Discharge ElectrolysisContact glow discharge electrolysis and polymerization in glow discharge plasma have been investigated to create of super-active species which might be hardly formed by conventional electrochemical methods.5) Synthetic Applications of Electrogenerated Active SpeciesThe potentialities of the electrogenerated active species in organic synthesis have been well demonstrated by synthesis of useful chemicals and natural products, e.g., cedran-type sesquiterpene, (-) -emetine and so on.