Organic Reactions Directed toword Organic Synthesis by the New Function of Highly Coordinated Transition Metal Complexes

在过渡金属配合物中，有机铜化合物在有机合成中得到了广泛的研究和应用，并且使用这些物种的反应主要基于它们的烷基化能力。在这些烷基化反应中，还原很少作为副反应发生。在仅发生还原过程的情况下，铜酸盐的这种还原性质已被用于直接生成有机铜试剂。有机锰试剂也被报道为烷基化试剂。我们发现的烯醇化物的生成从羰基化合物携带一个离去基团，如乙酰氧基，甲硅烷氧基，或卤素基团在a位置通过使用的有机锰（II）酸盐配合物和它们的特征反应与亲电试剂。由烯丙基溴和炔丙基溴生成烯丙基锰试剂和炔丙基锰试剂，并通过碘甲基硫醚和锰酸盐络合物作为还原剂的反应直接生成硫甲基锰试剂。这些试剂与各种亲电试剂反应。在α-卤代酮和酯的反应中，铬酸盐络合物也表现为还原剂，以生成与羰基化合物和烷基卤化物有效反应的铬烯醇化物。在与烯丙基或炔丙基磷酸酯的反应中，可以得到相应的铬试剂。

Among transition metal ate complexes, the organocuprates have been predominantly investigated and utilized in organic synthesis, and reactions using these species are mainly based on their alkylating abilities. The reduction rarely takes place as a side reaction in these alkylations. This reductive nature of cuprates has been utilized for the direct generation of organocopper reagents in the cases where only a reductive process occurs. The organomanganese reagents were also reported to be alkylating agents. We found the generation of the enolates from the carbonyl compounds bearing a leaving group such as an acetoxy, siloxy, or halogen group at the a position by using the organomanganese(II) ate complexes and their characteristic reactions with electrophiles. From allyl and propargyl bromides, allyl- and propargylmanganese reagents were generated, and the direct generation of thiomethylmanganese reagents was also attained by the reaction of iodomethylsulfides and the manganese ate complex as a reductant. These reagents reacted with a variety of electrophiles. Chromium ate complexes also behaved as a reductant in the reaction of a-halo ketones and esters to generate chromium enolates that react with carbonyl compounds and alkyl halides efficiently. In the reactions with allyl or propargyl phosphates, the corresponding chromium reagents could be obtained.