PHOTOINDUCED TRANSFORMATION OF CARBONYL COMPOUNDS UTILIZING SELECTIVE INTERACTION WITH AMINES

在本研究中，我们首先研究了羰基化合物与胺类化合物光反应产生的离子自由基对相互作用的性质。然后我们着重研究了几种底物的还原转化和新的给电子体化合物的合成。通过这些努力，获得了如下所述的一些有趣的观察结果。例如，溴甲基取代的苯并环酮和各种胺的光反应显示，反应过程中衍生自这些化合物的自由基中间体的选择性受到所涉及的胺阳离子自由基的性质的显着影响。特别是，这些羰基化合物与1，3-二甲基-2-苯基苯并咪唑啉（DMPBI）的光反应是值得注意的。这些底物产生的中间碳自由基可从DMPBI阳离子自由基上夺取氢原子，生成所观察到的产物。另一方面，DMPBI可以还原相同的碳自由基 ...更多信息 DMPBI阳离子自由基通过加入碱去质子化而产生的自由基，通过质子化变成碳负离子，得到相同的产物。在与我们的目的的开发高效和选择性的光转化使用DMPBI及其衍生物，我们进行了光还原的环氧酮与DMPBI和乙酸的组合，以产生所需的羟基酮在良好的产率。在该反应中，首先成功地分离了氧化的DMPBI，1，3-二甲基-2-苯基苯并咪唑鎓盐。2-合成了萘基和2-蒽基取代的1，3-二甲基苯并咪唑啉类化合物，并发现它们对羰基化合物的光诱导还原反应具有良好的催化活性。为了寻找适用于上述光化学体系的新底物，还进行了几种羰基化合物的二碘化钐还原反应。然后，前所未有的分子内的酮自由基的亲核反应性被发现。我们希望我们在这一领域和相关领域的持续研究将使我们能够开发新的光诱导电子转移反应系统使用DMPBI及其类似物。少

In this research, we first investigated the nature ot the interaction of the ion radical pairs generated by photoreaction of carbonyl compounds and amines. We then paid our attention to the reductive transformation ot several substrates and the synthesis of new electron donor compounds. Through these efforts, several interesting observations were obtained as described below. For example, photoreaction of bromomethyl substituted benzocyclic ketones and various amines revealed that the selectivity of the reaction course for the radical intermediates derived from these compounds was significantly influenced by the nature of the amine cation radicals involved. Particularly, photoreaction of these carbonyl compounds with 1,3-dimethyl-2-phenylbenzimidazoline (DMPBI) was noteworthy. The Intermediate carbon radicals derived from these substrates could abstract hydrogen atom from DMPBI cation radical to afford observed products. On the other hand, same carbon radicals could be reduced by DMPBI … More radical generated from the deprotonation of DMPBI cation radical by added bases to become the carbanions giving same products through protonation. In the connection with our purpose of the development of highly efficient and selective phtotransformation using DMPBI and its derivatives, we conducted photo-reduction of epoxy ketones with the combination of DMPBI and acetic acid to produce desired hydroxy ketones in good yields. In this reaction, isolation of the oxidized DMPBI, 1,3-dimethyl-2-phenylbenzimidazolium salt was first succeeded. 2-Naphthyl and 2-anthryl substituted 1,3-dimethylbenziimidazolines were synthesized and were found to be effective for the photoinduced reduction of some carbonyl compounds. In order to find new substrates which could be applicable to the above phtochemical systems, samarium diiodide reduction of several carbonyl compounds were also conducted. Then, unprecedented intramolecular nucleophilic reactivity of ketyl radicals was discovered. We hope that our continuous investigation in this and the related areas will allow us to develop new photoinduced electron transfer reaction systems using DMPBI and its analogues. Less