【摘要】：手性與生命現(xiàn)象休戚相關(guān),通過(guò)手性催化劑進(jìn)行不對(duì)稱催化合成反應(yīng)是獲得手性化合物最有效的方法。本文進(jìn)行了不對(duì)稱羰基化反應(yīng)(不對(duì)稱氫羧基化、不對(duì)稱氫酯基化、不對(duì)稱氫甲�；�)工藝研究,得到了上述三種手性羰基化反應(yīng)的較佳反應(yīng)工藝條件;首次采用了銠-膦手性離子液體催化劑催化芳基烯烴不對(duì)稱氫甲酰化反應(yīng),實(shí)現(xiàn)了貴金屬的循環(huán)利用。通過(guò)研究確定1-苯基乙醇不對(duì)稱氫羧基化反應(yīng)的較佳反應(yīng)條件為:主催化劑PdCl2;助催化劑CuCl2;手性配體BNPPA((S)-(+)-1,1'-聯(lián)萘-2,2'-二基磷酸氫酯);溶劑甲苯;反應(yīng)溫度100?C;CO壓力5 MPa;反應(yīng)時(shí)間22 h;主催化劑用量Pd/S(摩爾比,S為底物)=0.07;配體用量P/Pd=3;助催化劑用量Cu/Pd=6。在此反應(yīng)工藝條件下1-苯基乙醇轉(zhuǎn)化率為94%,2-苯基丙酸收率為84%,異正比為95/5,e.e.值為18%。實(shí)驗(yàn)確定苯乙烯不對(duì)稱氫酯基化反應(yīng)的較佳反應(yīng)條件為:主催化劑PdCl2;助催化劑CuCl2;手性配體BNPPA((S)-(+)-1,1'-聯(lián)萘-2,2'-二基磷酸氫酯);溶劑甲苯;反應(yīng)溫度80?C;CO壓力4 MPa;反應(yīng)時(shí)間14 h;主催化劑用量Pd/S=0.05;配體用量P/Pd=3;助催化劑用量Cu/Pd=6。在此反應(yīng)工藝條件下苯乙烯轉(zhuǎn)化率為93%,2-苯基丙酸甲酯收率為82%,異正比為94/6,e.e.值為43%。實(shí)驗(yàn)確定苯乙烯不對(duì)稱氫甲酰化反應(yīng)較佳反應(yīng)條件為:催化劑Rh(acac)(CO)2;手性配體(R,R)-Ph-BPE[(-)-1,2-雙((2R,5R)-2,5-二苯基磷)乙烷];溶劑甲苯;反應(yīng)溫度60?C;合成氣(CO/H2=1)壓力2 MPa;反應(yīng)時(shí)間4 h;催化劑用量Rh/S=1/2000;配體用量P/Rh=4。在此反應(yīng)工藝條件下苯乙烯轉(zhuǎn)化率為100%,2-苯基丙醛收率為96%,異正比為98/2,e.e.值為67%。本文以合成的咪唑類鹽離子液體[Bmim]Cl與羰基銠鹽K[Rhx(CO)y]進(jìn)行陰陽(yáng)離子置換形成功能化離子液體[Bmim][Rhx(CO)y]。銠-膦手性離子液體催化劑由苯乙烯不對(duì)稱氫甲酰化過(guò)程中功能化離子液體[Bmim][Rhx(CO)y]與手性配體(R,R)-Ph-BPE原位合成;并研究確定了較佳的苯乙烯不對(duì)稱氫甲�；磻�(yīng)條件。在溶劑甲苯;反應(yīng)溫度80?C;合成氣(CO/H2=1)壓力2 MPa;反應(yīng)時(shí)間4 h;底物為9.6 mmol時(shí)羰基銠離子液體催化劑用量[Bmim][Rhx(CO)y]0.6 g;手性配體用量(R,R)-Ph-BPE19 mg(0.0384 mmol),對(duì)苯二酚5 mg的反應(yīng)工藝條件下,苯乙烯轉(zhuǎn)化率為82%,2-苯基丙醛收率為60%,e.e.值為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，

本文編號(hào)：2408288