Development of Synthetic Organic Reactions Based on Novel Characteristic Behavior of Highly Coordinated Transition Metal Complexes

与基于主族元素的ATE络合物不同，过渡金属ATE络合物除了烷基化试剂外，还可能是还原剂，因为ATE络合物的电子过剩体系可以通过氧化加成与亲电体反应。我们计划研究过渡金属络合物的还原行为，发现有机金属试剂从几个亲电离子开始直接和还原生成，然后三丁基锰酸盐试剂与碘甲基硫化物反应生成相应的硫代甲基锰试剂。在该反应中，金属-卤素交换反应即使在-78℃也迅速进行，而碘甲硫化物与锰酸盐络合物的氧化加成主要在-20℃进行。硫甲基锰试剂与烯丙基溴化物、烯酮和醛反应。铬酸络合物还还原烯丙基磷酸盐生成烯丙基铬试剂。我们还发现了铁催化的炔烃碳化反应，在那里产生了区域和立体化学定义的多取代乙烯基锂试剂。在该反应中，基于低价铁的ATE-型络合物被认为是一种实际的催化剂。

In contrast to ate-complexes based on main-group elements, transition-metal ate complexes are expected to be reductants besides alkylating agents, since the ate-complexes, the electron-excess system may react with electrophiles through the oxidative addition. We planed to investigate the reductive behavior of the transition metal ate complexes and found the direct and reductive generation of organometallic reagents starting from several electrophiles.Thus tributylmanganate reagent reacted with iodomethyl sulfides to produce the corresponding thiomethylmanganese reagents. In this reaction, metal-halogen exchange reaction proceeds rapidly even at-78℃, while the oxidative addition of iodomethyl sulfide to the manganese ate complex takes place predominantly at -20℃. Thiomethylmanganese reagents react with allyl bromides, enones, and aldehydes.Chromium ate complexes also reduce allyl phosphates to generate allylchromium reagents. We also found iron-catalyzed carbolithiation of alkynes, where the regio-and stereochemically defined multi-substituted vinyllithium reagents were produced. In this reaction, ate-type complex based on low valent iron is thought to be an actual catalyst.