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

1.作为一种新的还原剂的锰酸盐络合物：完全区域控制的生成和与亲电性的反应锰酸盐(II)络合物干净地与在α位置带有离开基团的羰基化合物反应生成原酮、酯和酰胺的烯醇酸盐，无论它们的结构如何，其中锰酸盐作为还原剂而不是烷基化试剂。在这种基于锰酸盐络合物新的反应性的烯醇酸盐的还原生成中，底物的一种氧化加成和配体在锰上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。该反应的共性不仅表现在芳香酮和脂肪酮的烯醇化产物中，而且表现在脂肪族…的生成中更多的酯和酰胺。在合成价值方面，该反应被成功地应用于一对与不对称和非支链脂肪酮相对应的区域异构体烯醇酸酯的生成和反应。2.没有先例的Sm介体反应：生成非稳定的羰基Ylids Sm显示出很强的还原能力，并凭借其亲氧性被广泛应用于有机合成中，形成碳-碳键和转化各种具有高选择性的官能团。在对活性物种的生成和反应的研究过程中，我们报道了一种新的活性物种--非稳定的羰基叶立德的生成。这些活性物种在Sm的作用下是不可接近的，并且它们的[3+2]环加成反应是在多种不饱和化合物上进行的，如醛、烯、烯和炔。3.含羟基的乙烯基硅烷在酸的催化下进行了硅定向环化反应，得到了四氢呋喃和四氢吡喃，而羟基与乙烯基硅烷的加成反应以立体选择性的方式进行。较少

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