Development of Bismuth Compounds as A Organic Synthetic Reagent and It's Application to New Synthetic Reactions

使用铋的有机合成描述如下1.三丁基铋的酯化反应：在氧气气氛下，三丁基铋与酸性氯化物或羧酸反应，以较高的产率得到相应的羧酸丁酯。催化三氟化铋促进立体选择性的羟醛反应：在催化量的三氟化铋存在下，硅烯醇醚与醛反应，以良好的产率得到相应的醇醇。当苯丙酮的硅烯醇醚与醛反应时，可得到立体选择性的赤霉醇产品。手性酒石酸二乙酯-三氟化铋不对称羟醛缩合反应得到的产物光学产率较低(ee仅为12%)。在金属铋存在下，炔丙基溴与醛的反应：在金属铋的存在下，炔丙基溴与醛反应生成Allen衍生物和乙炔衍生物的混合物。三氯化铋催化环氧化物氨解合成β-氨基醇：在三氯化铋存在下，环氧化物与芳香胺反应生成相应的β-氨基醇。手性铋化合物催化醛的不对称三甲基硅基氰化反应：用三氯化铋或三氟化铋定量地对多种醛进行三甲基硅基氰化反应。以手性酒石酸二乙酯、丁基锂和三氯化铋为原料，原位合成了2-羟基-2-苯基乙腈。三氯化铋催化下烯丙基三甲基硅烷与醛反应合成吡喃衍生物：在三氯化铋存在下，烯丙基三甲基硅烷与2当量的醛反应生成吡喃衍生物。三氯化铋-金属锌催化亚胺的烯丙化反应：在三氯化铋-金属锌存在下，丙烯基溴与亚胺反应生成相应的高烯丙基胺。

Organic synthesis by using bismuth is described as follows.1. Esterification Reaction Using Tributylbismuthine : Under an oxygen atmosphere, tributylbismuthine reacted with acid chlorides or carboxylic acids to give the corresponding butyl carboxylates in good yields.2. Catalytic Bismuth Triflate Promoted Stereoselective Aldol Reaction : In the presence of a catalytic amount of bismuth triflate, silyl enol ethers react with aldehydes to give the corresponding aldols in good yields. When the silyl enol ether of propiophenone was reacted with aldehydes, erythro aldol products were obtained stereoselectively. Asymmetric aldol reaction by chiral diethyl tartrate-bismuth triflate gave the product in low optical yield(only 12%ee).3. Reaction of Propargyl Bromide with Aldehydes in the Presence of Metallic Bismuth : In the presence of metallic bismuth, propargyl bromide reacted with aldehydes to give a mixture of the allen derivatives and acetylene derivatives.4. Synthesis of beta-Aminoalcohols by Bismuth Trichloride Mediated Aminolysis of Epoxides : In the presence of bismuth trichloride, epoxides reacted with aromatic amines to give the corresponding beta-aminoalcohols.5. Enantioselective Trimethylsilylcyanation of Aldehydes Catalyzed by Chiral Bismuth Compound : A variety of aldehydes were trimethylsilylcyanated in quantitative yields with bismuth trichloride or bismuth triflate. 2-Hydroxy-2-phenylacetonitrile was obtained in 58% ee with a catalyst prepared in situ from chiral diethyl tartrate, butyllithium, and bismuth trichloride.6. Synthesis of Pyran Derivatives from Allyltrimenthylsilane and Aldehydes in the Presence of Bismuth Trichloride : In the presence of bismuth trichloride, allyltrimenthylsilane reacted with 2 equivalents of aldehydes to afford pyran derivatives.7. Allylation of lmines by Using Bismuth Trichloride-Metallic Zinc : Allyl bromide reacted with imines to give the corresponding homoallylamines in the presence of bismuth trichloride-metallic zinc.