Development of Grignard-Type Addition Reaction and Application of Its into the Practical Synthetic Process

本文综述了格氏加成反应的发展及其在实际合成中的应用研究结果：1）在金属铋存在下烯丙基卤与醛的烯丙基化反应; 2）三氯化铋-金属锌-烯丙基溴与烯丙基单元对含羧基羰基化合物的格氏加成反应; 3）烯丙基与含羧基羰基化合物的格氏加成反应。在金属铋存在下烯丙醇原位生成烯丙基卤化物用于醛的烯丙基化反应。4）在金属镁/铋络合物体系中醛的一种新的水相Barbier-Grignard型烯丙基化反应。5）用烯丙基格氏试剂和各种金属盐在水介质中进行羰基化合物的烯丙基化反应。6）用烯丙基锡化合物和烯丙基铋化合物在水介质或水中进行醛的烯丙基化反应。7）用四烯丙基锡进行羰基化合物的不对称烯丙基化反应。8）双酚A介导的未保护碳水化合物的烯丙基化反应。9）在甲醇、含水有机溶剂或水中使用三丁基氢化锡进行溶剂介导的醛的化学选择性还原：一种环境友好的过程。10）在硅胶上使用三丁基氢化锡原位还原醛和苯胺生成的亚胺的无溶剂一锅法。

This summary presents the research results of development of Grignard-type addition reaction and application of its into the practical synthetic process.1) Allyation of aldehydes by using allylic halides in the presence of metallic bismuth.2) A Grignard-type addition of allyl unit to carbonyl compounds containing a carboxyl group by using bismuth trichloride-metallic zinc-allyl bromide.3) Allylation of aldehydes by using allylic halides prepared in situ from allylic alcohols in the presence of metallic bismuth.4) A novel aqueous Barbier-Grignard-type allylation of aldehydes in a metallic magnesium/bismuth trichloride bimetal system.5) Allylation of carbonyl compounds by using allyl Grignard reagent and various metallic salts in aqueous media.6) Allylation of aldehydes by using allyltin compounds and allylbismuth compounds in aqueous media or water.7) Asymmetric allylation of carbonyl compounds by using tetraallyltin.8) Bismuth mediated allylation of unprotected carbohydrates.9) Solvent-mediated chemoselective reduction of aldehydes by using tributyltin hydride in methanol, aqueous organic solvents, or water: an environmentally benign process.10) Solvent-free one-pot reduction of imines generated in situ from aldehydes and aniline by tributyltin hydride on silica gel.