Chemistry and Synthetid Applications of Reactive Species Generated by Redox and Related Reactions of Organometallic Compounds

对课题进行了调查，取得了以下成果。通过研究14族有机金属化合物与二氰基化合物和铜(II)离子的光诱导电子转移，以及在有机碘化合物存在下缺电子烯烃与缺电子烯烃的反应，发展了新的反应，如二氰基芳烃中的氰基被烯丙基和苄基取代，这些基团加入到二氰基芳烃和二氰基烯烃中，第14族有机金属化合物的氧化裂解，以及缺电子烯烃的双C-C键形成反应。以低价钛配合物为催化剂，实现了烷二烯、烯丙醇和含氧不饱和化合物的区域和立体选择性氢化反应。新的反应，如N-酰氧亚胺化合物的还原脱氧，碳负离子的三重CO插入，烯丙基化合物上的亲电和亲核反应，以及&lt；α&gt；&lt；β&gt；-不饱和羰基化合物通过铁羰基络合物和(&lt；eta&gt；^3-烯丙基)Fe(CO)_2NO络合物的反应。介绍了上述反应的机理特点和合成应用，以及所涉及的反应物种的反应活性。

The titled subject have been investigated and the following results have been obtained.1. Novel reactions such as the substitution of CN group in dicyanoaromatics by allylic and benzylic groups, the addition of these groups to dicyanoaromatics and dicyanoalkenes, the oxidative cleavage of group 14 organometallics, and the double C-C bond-forming reactions of electron-deficient alkenes were developed by studying the photoinduced electron-transfer from the group 14 organometallics to the dicyano compounds and Cu(II) ions, and also by studying the reactions of the electron-deficient alkenes with allylic stannanes in the presence of organoiodo compounds.2. The regio- and stereo-selective hydroboration of alkadienes, allylic alcohols, and oxygen-containing unsaturated compounds were developed by use of lowvalent Ti-complexes as a catalyst.3. New reactions such as the reductive deoxygenation of N-acyloxyimino compounds, the triple CO insertion to carbanions, the electrophilic and nucleophilic reactions on allylic compounds and <alpha><beta>-unsaturated carbonyl compounds via iron carbonyl complexes and (<eta>^3-allylic)Fe(CO)_2NO complexes.4. The mechanistic features and synthetic applications of the above reactions, and also the reactivities of the reactive species involved were described.