不对称羰基化合成手性芳基丙酸酯的研究
发布时间：2019-01-13 08:50
【摘要】：手性与生命现象休戚相关,通过手性催化剂进行不对称催化合成反应是获得手性化合物最有效的方法。本文进行了不对称羰基化反应(不对称氢羧基化、不对称氢酯基化、不对称氢甲酰化)工艺研究,得到了上述三种手性羰基化反应的较佳反应工艺条件;首次采用了铑-膦手性离子液体催化剂催化芳基烯烃不对称氢甲酰化反应,实现了贵金属的循环利用。通过研究确定1-苯基乙醇不对称氢羧基化反应的较佳反应条件为:主催化剂PdCl2;助催化剂CuCl2;手性配体BNPPA((S)-(+)-1,1'-联萘-2,2'-二基磷酸氢酯);溶剂甲苯;反应温度100?C;CO压力5 MPa;反应时间22 h;主催化剂用量Pd/S(摩尔比,S为底物)=0.07;配体用量P/Pd=3;助催化剂用量Cu/Pd=6。在此反应工艺条件下1-苯基乙醇转化率为94%,2-苯基丙酸收率为84%,异正比为95/5,e.e.值为18%。实验确定苯乙烯不对称氢酯基化反应的较佳反应条件为:主催化剂PdCl2;助催化剂CuCl2;手性配体BNPPA((S)-(+)-1,1'-联萘-2,2'-二基磷酸氢酯);溶剂甲苯;反应温度80?C;CO压力4 MPa;反应时间14 h;主催化剂用量Pd/S=0.05;配体用量P/Pd=3;助催化剂用量Cu/Pd=6。在此反应工艺条件下苯乙烯转化率为93%,2-苯基丙酸甲酯收率为82%,异正比为94/6,e.e.值为43%。实验确定苯乙烯不对称氢甲酰化反应较佳反应条件为:催化剂Rh(acac)(CO)2;手性配体(R,R)-Ph-BPE[(-)-1,2-双((2R,5R)-2,5-二苯基磷)乙烷];溶剂甲苯;反应温度60?C;合成气(CO/H2=1)压力2 MPa;反应时间4 h;催化剂用量Rh/S=1/2000;配体用量P/Rh=4。在此反应工艺条件下苯乙烯转化率为100%,2-苯基丙醛收率为96%,异正比为98/2,e.e.值为67%。本文以合成的咪唑类盐离子液体[Bmim]Cl与羰基铑盐K[Rhx(CO)y]进行阴阳离子置换形成功能化离子液体[Bmim][Rhx(CO)y]。铑-膦手性离子液体催化剂由苯乙烯不对称氢甲酰化过程中功能化离子液体[Bmim][Rhx(CO)y]与手性配体(R,R)-Ph-BPE原位合成;并研究确定了较佳的苯乙烯不对称氢甲酰化反应条件。在溶剂甲苯;反应温度80?C;合成气(CO/H2=1)压力2 MPa;反应时间4 h;底物为9.6 mmol时羰基铑离子液体催化剂用量[Bmim][Rhx(CO)y]0.6 g;手性配体用量(R,R)-Ph-BPE19 mg(0.0384 mmol),对苯二酚5 mg的反应工艺条件下,苯乙烯转化率为82%,2-苯基丙醛收率为60%,e.e.值为10%。
[Abstract]:Chirality is closely related to life phenomena. Asymmetric catalytic synthesis with chiral catalysts is the most effective way to obtain chiral compounds. In this paper, the asymmetric carbonylation reaction (asymmetric hydrocarboxylation, asymmetric hydroesterification, asymmetric hydroformylation) has been studied, and the better reaction conditions for these three chiral carbonylation reactions have been obtained. The asymmetric hydroformylation of aryl olefin catalyzed by rhodium-phosphine chiral ionic liquid catalyst was used for the first time to realize the recycling of precious metals. The optimum reaction conditions for asymmetric hydrocarboxylation of 1-phenylethanol were determined as follows: the main catalyst PdCl2; cocatalyst CuCl2; chiral ligand BNPPA (S)-() -1 ~ (1) -1 ~ (1) -binaphthalene ~ (2) -2o _ (2) -diphenyl hydrogen phosphate); Solvent toluene; reaction temperature 100g CO pressure 5 MPa; reaction time 22 h; amount of main catalyst Pd/S (molar ratio, S as substrate) = 0.07; dosage of ligand P / PdN 3; amount of co-catalyst Cu/Pd=6. Under this reaction condition, the conversion of 1-phenylethanol was 94 and the yield of 2-phenylpropionic acid was 84. The ratio of heterogeneity was 95 / 5. The value is 18. The optimum reaction conditions for the asymmetric hydrogenation of styrene were determined as follows: the main catalyst PdCl2; co-catalyst CuCl2; chiral ligand BNPPA (S)-() -1- (1) -bina- (2) -diphenyl hydrogen phosphate), the solvent toluene; Reaction temperature 80 鈩，
本文编号：2408288
[Abstract]:Chirality is closely related to life phenomena. Asymmetric catalytic synthesis with chiral catalysts is the most effective way to obtain chiral compounds. In this paper, the asymmetric carbonylation reaction (asymmetric hydrocarboxylation, asymmetric hydroesterification, asymmetric hydroformylation) has been studied, and the better reaction conditions for these three chiral carbonylation reactions have been obtained. The asymmetric hydroformylation of aryl olefin catalyzed by rhodium-phosphine chiral ionic liquid catalyst was used for the first time to realize the recycling of precious metals. The optimum reaction conditions for asymmetric hydrocarboxylation of 1-phenylethanol were determined as follows: the main catalyst PdCl2; cocatalyst CuCl2; chiral ligand BNPPA (S)-() -1 ~ (1) -1 ~ (1) -binaphthalene ~ (2) -2o _ (2) -diphenyl hydrogen phosphate); Solvent toluene; reaction temperature 100g CO pressure 5 MPa; reaction time 22 h; amount of main catalyst Pd/S (molar ratio, S as substrate) = 0.07; dosage of ligand P / PdN 3; amount of co-catalyst Cu/Pd=6. Under this reaction condition, the conversion of 1-phenylethanol was 94 and the yield of 2-phenylpropionic acid was 84. The ratio of heterogeneity was 95 / 5. The value is 18. The optimum reaction conditions for the asymmetric hydrogenation of styrene were determined as follows: the main catalyst PdCl2; co-catalyst CuCl2; chiral ligand BNPPA (S)-() -1- (1) -bina- (2) -diphenyl hydrogen phosphate), the solvent toluene; Reaction temperature 80 鈩，
本文编号：2408288
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