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过程中的应用。1)金属铋存在下烯丙基卤化物催化醛的格氏加成反应。2)三氯化铋-金属氯化锌-烯丙基溴化物催化烯丙基单元与含羧基的羰基化合物的格氏加成反应。3)金属铋存在下烯丙基卤化物催化醛的烯丙化反应。4)金属镁/三氯化铋体系中醛的巴氏-格氏加成反应在水介质中使用烯丙基格氏试剂和各种金属盐。6)在水介质或水中使用烯丙基锡化合物和烯丙基铋化合物进行醛的烯丙化反应。7)通过使用四烯丙基锡对羰基化合物进行不对称的烯丙化反应。8)铋催化无保护的碳水化合物的烯丙化反应。9)通过在甲醇中使用三丁基锡氢化物的溶剂介导醛的化学选择性还原，水性有机溶剂，或水：一种环保的过程。10)三丁基锡氢化物在硅胶上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.