Creation of Highly Functional Reagents and its Application to Novel Organic Synthesis

在本研究项目中获得了以下结果：锰酸盐配合物作为一种新的还原剂：锰酸盐配合物与亲电性烯醇酸盐的完全区域控制生成和反应锰酸盐配合物与α位置有离去基的羰基化合物反应，生成原始酮、酯和酰胺的烯醇酸盐，而不考虑其结构，其中锰酸盐作为还原剂而不是烷基化剂。在这种基于锰酸盐配合物新反应性的烯醇酯的还原生成过程中，一种底物的氧化加成和锰上配体的还原消除可能是关键过程，而相当于“金属-卤素交换”的过程似乎并不重要。该反应的普遍性不仅体现在芳香族酮和脂肪族酮的烯醇化产物的生成上，而且还体现在脂肪族更多的酯和酰胺的生成上。在合成价值方面，该反应成功应用于非对称非支链脂肪酮对应的一对区域异构体烯醇化物的完全区域特异性生成和反应。钐具有很强的还原能力，并凭借其亲氧性，被广泛应用于有机合成中碳-碳键的形成和各种高选择性官能团的转化。在我们对活性物质的生成和反应的研究过程中，我们报道了由钐介导的碘甲基硅醚生成的新的活性物质，非稳定羰基酰体，以及它们的[3+2]环加成到各种不饱和化合物，如醛、烯、烯和炔。含羟基乙烯基硅烷的硅定向环化酸催化含羟基乙烯基硅烷的酸催化环化得到了四氢呋喃和四氢吡喃，羟基在乙烯基硅烷上的加成以同步立体选择的方式进行。少

The following results are obtained in this research project.1.Manganese Ate Complexes as a New Reducing Agent : Perfectly Regiocontrolled Generation and Reactions of the Mn-Enolates with ElectrophilesManganese (II) ate complexes cleanly react with carbonyl compounds bearing a leaving group at the alpha position to generate the enolates of the original ketones, esters, and amides, irrespective of their structure, where the manganate serves as a reductant not an alkylation agent. In this reductive generation of the enolates based on the novel reactivity of the manganese ate complexes, a kind of oxidative addition of a substrate to the ate complex and the reductive elimination of the ligands on manganese are possibly involved as the key processes, while the process equivalent to "metal-halogen exchange" does not seem to be significant. The generality of this reaction was demonstrated in the generation of the enolates of not only aromatic ketones and aliphatic ketones but also an aliphatic … More ester and amide. As for the synthetic value, this reaction was successfully applied to the perfectly regiospecific generation and reactions of a pair of the regioisomeric enolates corresponding to the unsymmetrical and non-branched aliphatic ketones.2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsSamarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.3.Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an AcidThe acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyrans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion. Less