Development of New Synthetic Reactions by Rare Earth Metals

稀土金属新合成反应的进展

基本信息

批准号：
63550651
负责人：
FUJIWARA Yuzo
金额：
$ 1.02万
依托单位：
HIROSHIMA UNIVERSITY (1989)Kyushu University (1988)
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

By studies on this project, the following novel synthetic reactions have been found by utilizing samarium(Sm) and ytterbium(Yb) metals.1. Samarium Metal Promoted Selective Synthesis of Azoxy Compounds. We found that Sm metal can reduce various nitroarenes at room temperature to give the corresponding azoxy compounds selectively; a bromine, iodine, or carbonyl group in the substrates is retained. This method, because of its simplicity and high selectivity, constitutes a useful alternative to the commonly accepted procedures for the synthesis of azoxy compounds.2. Ytterbium Metal Mediated Synthesis of Unsymmetrical 1,2-Diols. We found that Yb metal reacts with diaryl ketones such as benzophenone, phenyl methyl ketone and 9-fluorenone to form metallaoxirane intermediates which further react with ketones and aldehydes to give the corresponding cross- coupling products, unsymmetrical 1,2-diols in high yields.Similarly, the metallaoxirane intermediate has been found to undergo nucleophilic addition to various electrophfles such as epoxides, nitriles, esters, CO_2 etc., to give the corresponding cross-coupling products. Because these reactions of Yb-umpoled ketones with electrophiles proceed under very mild conditions to give high yields, and have simplicity of the procedure, the present reactions constitute useful methods for the synthesis of not only unsymmetrical 1,2-diols but also 1,3-diols, alpha-hydroxy ketones, etc.Through this project, rare earth metals, the simplest reagent have been found to act as very useful synthetic reagents under mild conditions.

通过对该项目的研究，通过使用samarium（SM）和Ytterbium（YB）金属发现了以下新的合成反应。1。 samarium金属促进了硫代化合物的选择性合成。我们发现，SM金属可以在室温下降低各种硝化碳，以选择性地提供相应的azoxy化合物。保留了底物中的溴，碘或羰基。由于其简单性和高选择性，该方法构成了合成Azoxy Chipounds的普遍接受程序的有用替代方法。2。 ytterbium金属介导的不对称1,2-二醇的合成。 We found that Yb metal reacts with diaryl ketones such as benzophenone, phenyl methyl ketone and 9-fluorenone to form metallaoxirane intermediates which further react with ketones and aldehydes to give the corresponding cross- coupling products, unsymmetrical 1,2-diols in high yields.Similarly, the metallaoxirane intermediate has been found to undergo nucleophilic除各种电源，例如环氧化物，硝酸盐，酯，CO_2等，以提供相应的交叉耦合产物。因为在非常轻微的条件下进行高产量并具有简单性，目前的反应构成了综合不仅是不合格的1,2-二醇，还构成了1,3-二醇，alpha-hydroxy ketones of simply simplation confection构成了本反应，而稀有的综合是，这种反应构成了alpha-hydroxy kety kety keters of Simplation，构成了一个非常有用的综合，这是对YB的酮与电力的这些反应，并具有很小的收益率并具有简单性，因此目前的反应构成了有用的方法。在轻度条件下的试剂。