CN108774271B - 一种基于二茂铁骨架的手性氮氮膦三齿配体及其应用 - Google Patents
一种基于二茂铁骨架的手性氮氮膦三齿配体及其应用 Download PDFInfo
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Abstract
本发明属于不对称催化技术领域,具体涉及一种基于二茂铁骨架的手性氮氮膦三齿配体及其应用。本发明中公开的基于二茂铁骨架的手性氮氮膦三齿配体与过渡金属前体络合所得的配合物,并将该配合物作为贵金属催化剂,成功应用于芳香酮的高效不对称氢化。相比于其他三齿配体,该配体具有合成简单、对水和空气稳定、易于大规模制、对碳氧双键表现出了高活性和高对映选择性等特点,具有较大的实施价值和社会经济效益。
Description
技术领域
本发明属于不对称催化技术领域,具体涉及一种基于二茂铁骨架的手性氮氮膦三齿配体及其应用。
背景技术
手性是自然界的本质属性之一,使用手性药物、手性农药往往能达到更好的治疗或杀虫效果。不对称催化氢化,作为获取手性化合物的重要方法之一,具有原子经济性好、立体选择性高等优点,一直都是研究热点之一。
金属和手性配体的组合因具有优异的催化性能而成为不对称催化氢化的主流。早在20世纪70年代,William S.Knowles就利用金属铑和有机膦配体,首次实现不对称催化氢化,并将其应用于手性药物L-多巴的工业合成(Chem.Commun.1965,17)。日本化学家野依良治发明了手性双膦配体BINAP及其过渡金属催化剂,实现了不对称催化氢化反应,并将其应用于L-薄荷脑等手性药物的工业合成中(Acc.Chem.Res.1990,23,345)。之后的研究主要集中在双齿配体的研究上,而三齿配体的研究相对滞后。张绪穆课题组开发了以二茂铁为关键骨架的手性氮膦氧三齿配体,并成功应用于一系列简单酮的不对称氢化反应中。此类配体在获取高纯度R构型产物中表现出了超高活性,但是对于S构型产物,效果不尽如人意(Org.Lett.2017,19,2548-2551;Org.Lett.2017,19,690-693;Chem.Eur.J.2017,23,970–975;Org.Lett.2016,18,2938-2941;Org.Lett.2016,18,2938-2941;CN 105732725A.)。周其林院士也发展了一类手性螺环三齿配体,在简单酮的不对称氢化反应中表现出较高的活性(Angew.Chem.,Int.Ed.2011,50,7329)。但是此类螺环配体合成路线长,价格昂贵。相比已有的三齿配体,本发明提供了一类合成简单、对水和空气稳定、易于大规模制备的基于二茂铁骨架的手性氮氮膦三齿配体,该配体已在不对称氢化反应中表现出高活性和高选择性,能够选择性的得到S构型产物,与张绪穆研究小组报道的三齿配体正好互补,具有较广的工业化应用前景。
发明内容
针对现有技术中存在的上述问题,本发明的目的在于提供一种新型高活性高选择性催化不对称氢化反应及其类似反应的基于二茂铁骨架的手性氮氮膦三齿配体,该配体具有合成简单、对水和空气稳定、高活性和高选择性、易于实现工业化生产等特点。
所述的一种基于二茂铁骨架的手性氮氮膦三齿配体,其特征在于其结构通式如通式(I)或通式(II)所示:
通式(I)中:R1、R2独立为烷基、烷氧基、芳基、芳氧基或氢原子,R1、R2成环或不成环;R3为芳基、杂环芳基或烷基;X为(CH2)n,其中n为1到6的整数;
通式(II)中:R1、R2独立为烷基、烷氧基、芳基、芳氧基或氢原子,R1、R2成环或不成环;R3为芳基、杂环芳基或烷基;R4为烷基、芳基、杂芳基或氢。
本发明所述的部分优选三齿配体,每一个配体对应两种对映异构体,也是本发明实施例的内容,具体如下:
本发明中所述的基于二茂铁骨架的手性三齿配体可由廉价易得的Ugi-amine和手性二胺经数步反应高收率的获得,该配体对水和空气稳定,易于纯化,并且可以通过简单的基团改变来调控配体的位阻和电性,非常适合大规模制备,具有较高的工业化应用价值。
所述的一种贵金属催化剂,其特征在于为由权利要求1所述的基于二茂铁骨架的手性氮氮膦三齿配体与过渡金属前体络合所得的配合物,三齿配体与过渡金属前体在合适的溶剂(溶剂分子选自甲醇、乙醇、异丙醇、二氯甲烷、四氢呋喃和甲苯等中的一种)中络合0.5~2小时。
所述的贵金属催化剂,其特征在于过渡金属为Ru、Rh、Ir或Pd中任意的一种。
所述的贵金属催化剂,其特征在于过渡金属前体选自Pd(COD)Cl2、Pd(PPh3)4、PdCl2(PPh3)2、Pd(dba)2、Pd(OAc)2、PdCl2L2、[Rh(NBD)2]+BF4、[Rh(NBD)Cl]2、[Rh(COD)Cl]2、[Rh(COD)2]X、[Rh(acac)(CO)]2、Rh(ethylene)2(acac)、Rh(ethylene)2Cl2、RhCl(PPh3)3、Rh(CO)2Cl2、RuHX(L)2(diphosphine)、Ru(arene)X2(diphosphine)、Ru(aryl group)X2、Ru(RCO2)2(diphosphine)、Ru(methallyl)2(diphosphine)、Ru(aryl group)X2(PPh3)3、RuX2(L)2(diphosphine)、Ru(COD)(COT)、Ru(COD)(COT)X、RuX2(cymene)、Ru(aryl group)X2(diphosphine)、RuCl2(COD)、[Ru(COD)2]X、RuX2(diphosphine)、Ru(ArH)Cl2、Ru(COD)(methallyl)2、[Ir(NBD)2Cl]2、Ir(NBD)2)X、[Ir(COD)Cl]2或[Ir(COD)2]X中的任意一种。
所述的贵金属催化剂,其特征在于过渡金属前体R为烷基、烷氧基或取代的烷基,aryl为芳基,X为阴离子,X优选为BF4 -、ClO4 -、SbF6 -、PF6 -、CF3SO3 -、B(Ar)4 -,Ar为二(三氟甲基)苯或氟苯,L为溶剂分子,选自乙腈或苯甲腈。
所述的贵金属催化剂在不对称反应中的应用,特别是在简单酮的不对称氢化反应中,选择性地获得S构型手性醇。
所述的应用,其特征在于所述的不对称反应包括不对称氢化反应、不对称氢转移反应、不对称烯丙基化反应、不对称偶联反应、不对称环氧化反应和不对称环加成反应。
通过采用上述技术,本发明提供的一种新型基于二茂铁骨架的手性氮氮膦三齿配体,具有合成简单、对水和空气稳定、高活性和高选择性、易于实现工业化生产等特点,而且该配体可以通过简单的基团改变来调控配体的位阻和电性,非常适合大规模制备,具有较高的工业化应用价值,可应用于简单酮的不对称氢化反应中,选择性地获得S构型手性醇。
具体实施方式
下面通过实施例对本发明加以说明,但本发明不仅限与实施例。
实施例1:配体LI2的合成
将(S)-Ugi-amine 1(5.14g,20mmol)溶于50mL乙醚中,氮气保护以及冰盐浴冷却下,往反应体系中滴加正丁基锂(16mL,2.5mol/L),滴完后缓慢升至室温,搅拌反应3小时。冰盐浴冷却下滴加二苯基膦氯(8.82g,40mmol),滴完后缓慢升至室温,搅拌反应12小时。用饱和碳酸氢钠溶液淬灭反应,二氯甲烷萃取,无水硫酸钠干燥,浓缩、柱层析得化合物2(5.38g,61%)。
将化合物2(4.41g,10mmol)溶于8.0mL醋酐中,55℃下反应4小时。反应完毕,减压回收过量的醋酐,然后高真空条件下除去低沸点的杂质,得粗产物3,无需纯化,直接用于下一步。
反应瓶中加入粗产物3(0.46g,0.1mmol)和4(0.60g,0.2mmol),置换氮气后,加入5mL甲醇,50℃下反应12小时。浓缩、柱层析得黄色配体LI2(0.37g,53%)。
1H NMR(600MHz,CDCl3)δ7.52–7.46(m,2H),7.39–7.34(m,3H),7.14(m,1H),7.01(s,4H),6.91(s,2H),5.92(s,1H),4.48(s,1H),4.35–4.31(s,1H),4.05(m,5H),4.03(s,1H),3.69(s,1H),2.59(s,6H),2.31(s,3H),2.17–2.01(m,2H),1.92–1.84(m,1H),1.75(s,1H),1.43(m,5H),1.27(m,1H),0.96(m,2H),0.81–0.72(m,1H),-0.44(d,J=8.1Hz,1H).13CNMR(151MHz,CDCl3)δ141.45,140.03,139.95,138.98,136.43,136.36,135.03,134.86,134.19,132.59,132.44,131.68,129.14,128.31,128.26,128.12,128.06,74.05,74.00,71.03,71.00,69.62,69.31,69.28,69.14,57.66,56.89,46.18,31.93,29.70,24.78,23.87,23.03,20.86,19.80。
实施例2:配体LI3的合成
粗产物3的制备方法同实施例1。
反应瓶中加入粗产物3(0.46g,0.1mmol)和5(0.53g,0.2mmol),置换氮气后,加入5mL甲醇,50℃下反应15小时。浓缩、柱层析得黄色配体LI3(0.40g,51%)。
1H NMR(600MHz,CDCl3)δ7.48(m,2H),7.35(m,3H),7.15(s,2H),7.08(t,J=7.1Hz,3H),6.96(t,J=6.8Hz,2H),5.96(s,1H),4.50(s,1H),4.27(s,1H),4.08(m,1H),4.05(d,J=7.0Hz,1H),4.04(s,5H),4.03(d,J=6.8Hz,1H 1H),3.64(s,1H),3.02–2.92(m,1H),2.22–1.92(m,4H),1.49(t,J=10.2Hz,2H),1.39(d,J=5.4Hz,3H),1.28(dd,J=6.8,5.3Hz,6H),1.23(d,J=6.8Hz,6H),1.17(d,J=6.8Hz,6H),1.09–0.96(m,2H),0.14(s,1H),-0.20(d,J=11.5Hz,1H).13C NMR(151MHz,CDCl3)δ152.07,150.28,139.96,139.88,136.45,136.38,135.13,134.96,133.54,132.71,132.56,129.16,128.31,128.26,128.13,128.07,123.62,97.49,74.36,74.31,71.20,71.17,70.01,69.65,69.12,57.40,57.26,46.55,34.09,31.95,29.84,29.70,25.16,25.05,23.89,23.73,23.53,19.75。
实施例3:配体LI5的合成
(S)-Ugi-amine 1(2.57g,10mmol)溶于25mL乙醚中,氮气保护以及冰盐浴冷却条件下往反应体系中滴加正丁基锂(8mL,2.5mol/L),滴完后缓慢升至室温,搅拌反应3小时。冰盐浴冷却下滴加双(3,5-二叔丁基苯基)氯化磷(8.90g,20mmol),滴完后缓慢升至室温,搅拌反应24小时。用饱和碳酸氢钠溶液淬灭反应,二氯甲烷萃取,无水硫酸钠干燥,浓缩、柱层析得产物7(3.79g,57%)。
将化合物7(3.33g,5mmol)溶于4.0mL醋酐中,55℃下反应4小时。反应完毕,减压回收过量的醋酐,然后高真空条件下除去低沸点杂质,得粗产物8,无需纯化,直接用于下一步。
反应瓶中加入化合物8(0.68g,0.1mmol)和2(0.54g,0.2mmol),置换氮气后,加入5mL乙醇,于50℃下反应18小时。浓缩、柱层析得黄色配体LI5(0.54g,61%)。
1H NMR(600MHz,CDCl3)δ7.71(d,J=8.2Hz,2H),7.39(s,1H),7.31(d,J=8.3Hz,2H),7.26(s,1H),7.22(d,J=8.0Hz,2H),7.06(d,J=7.8Hz,2H),5.95(s,1H),4.48(s,1H),4.29(s,1H),4.08(s,5H),3.98(d,J=3.3Hz,1H),3.58(s,1H),2.40(s,3H),2.04(dd,J=17.2,11.3Hz,2H),1.94(m,1H),1.78(d,J=12.3Hz,1H),1.44(d,J=13.3Hz,1H),1.39(d,J=6.1Hz,4H),1.30(s,1H),1.28(s,18H),1.15(s,18H),1.03–0.90(m,2H),0.80–0.76(m,1H),-0.38(q,J=11.1Hz,1H).13C NMR(151MHz,CDCl3)δ150.74,150.70,150.09,150.05,142.64,138.13,138.08,135.27,135.22,129.43,129.25,129.11,127.50,127.36,127.14,122.84,122.30,109.70,76.14,76.10,70.92,70.90,69.61,68.86,57.65,47.10,34.90,34.74,31.52,31.47,31.43,31.34,30.00,25.08,23.84,21.53,20.77。
实施例4:配体LI8的合成
(S)-Ugi-amine 1(2.57g,10mmol)溶于25mL乙醚中,氮气保护以及冰盐浴冷却条件下往反应体系中滴加正丁基锂(8mL,2.5mol/L),滴完后缓慢升至室温,搅拌反应3小时。冰盐浴冷却下滴加双(3,5-二甲基苯基)氯化磷(5.53g,20mmol),滴完后缓慢升至室温,搅拌反应24小时。用饱和碳酸氢钠溶液淬灭反应,二氯甲烷萃取,无水硫酸钠干燥,浓缩、柱层析得产物10(3.03g,61%)。
将化合物10(2.49g,5mmol)溶于4.0mL醋酐中,55℃下反应4小时。反应完毕,减压回收过量的醋酐,然后高真空条件下除去低沸点杂质,得粗产物8,无需纯化,直接用于下一步。
反应瓶中加入化合物11(0.51g,0.1mmol)和4(0.60g,0.2mmol),置换氮气后,加入5mL甲醇,于50℃下反应18小时。浓缩、柱层析得黄色配体LI8(0.47g,63%)。
1H NMR(600MHz,CDCl3)δ7.14(d,J=8.2Hz,2H),7.01(s,1H),6.88(s,2H),6.85(s,1H),6.73(s,2H),5.96(s,1H),4.46(s,1H),4.31(s,1H),4.05(s,5H),4.01(s,1H),3.71(s,1H),2.60(s,6H),2.32(s,6H),2.26(s,3H),2.11(s,6H),2.03(s,2H),1.90(s,1H),1.80(d,J=12.2Hz,1H),1.42(m,5H),1.33–1.23(m,2H),0.97(m,4.1Hz,2H),0.81(m,1H),0.38–0.09(m,1H),-0.38(s,1H).13C NMR(151MHz,CDCl3)δ141.53,139.51,139.45,138.88,137.96,137.92,137.50,137.45,136.26,136.20,134.68,132.77,132.63,131.80,130.92,130.66,130.53,130.07,77.27,77.06,76.84,75.00,74.95,71.17,69.68,69.35,69.11,57.84,57.38,46.70,31.60,31.28,29.82,25.00,23.92,22.94,22.67,21.37,21.15,20.90,20.44,14.14。
实施例5:配体LI9的合成
粗产物8的制备方法同实施例3
反应瓶中加入化合物8(0.68g,0.1mmol)和4(0.60g,0.2mmol),置换氮气后,加入5mL甲醇,于50℃下反应18小时。浓缩、柱层析得黄色配体LI9(0.51g,56%)。
1H NMR(400MHz,CDCl3)δ7.41(s,1H),7.33(dd,J=6.8,1.0Hz,2H),7.28(d,J=1.8Hz,1H),7.06(d,J=5.8Hz,2H),6.88(s,2H),6.03(s,1H),4.49(s,1H),4.32(s,1H),4.11(s,5H),4.01(dd,J=4.6,2.2Hz,1H),3.60(s,1H),2.61(s,6H),2.28(s,3H),2.09–2.01(m,2H),1.90(t,J=8.0Hz,1H),1.71(d,J=9.1Hz,1H),1.47(d,J=4.9Hz,3H),1.40–1.35(m,1H),1.31–1.27(m,20H),1.16(s,18H),1.00–0.92(m,2H),0.76(dd,J=21.2,10.6Hz,1H),-0.52(q,J=10.9Hz,1H).13C NMR(100MHz,CDCl3)δ149.76,149.71,149.09,149.03,140.26,137.72,137.18,137.13,134.14,134.08,133.75,130.82,128.26,128.09,126.29,126.13,121.83,121.45,96.11,95.93,76.28,76.02,75.77,75.03,69.79,68.60,68.27,67.89,56.86,56.68,46.20,46.12,33.86,33.68,30.42,30.37,30.14,29.02,24.18,22.76,21.86,19.89,19.80,13.11。
实施例6:配体LII4的合成
粗产物11的制备方法同实施例4
反应瓶中加入化合物11(0.51g,0.1mmol)和12(0.73g,0.2mmol),置换氮气后,加入5mL甲醇,于50℃下反应18小时。浓缩、柱层析得黄色配体LII4(0.64g,65%)。
1H NMR(400MHz,CDCl3)δ7.32(d,J=6.5Hz,2H),7.26(d,J=6.8Hz,2H),7.13–7.07(m,3H),7.06–6.91(m,11H),6.62(d,J=6.0Hz,2H),6.51(s,1H),4.28–4.23(m,2H),4.20(t,J=4.3Hz,1H),3.93(d,J=4.8Hz,1H),3.89(s,6H),3.79(d,J=4.6Hz,1H),2.38(s,6H),2.33(s,3H),2.31(s,6H),1.07(d,J=5.3Hz,3H).13C NMR(100MHz,CDCl3)δ142.08,141.10,140.32,139.68,137.82,137.68,137.58,137.53,137.26,137.20,133.10,132.93,130.76,130.54,130.39,129.72,128.84,127.85,127.74,127.40,126.98,126.87,126.82,98.70,98.52,77.29,77.03,76.78,74.66,71.49,69.57,69.04,68.87,65.39,63.61,60.37,53.43,49.87,22.31,21.44,21.40,21.38。
实施例7:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI2(16.6mg,0.024mmol),金属[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得120mg产物(S)-1-苯-1-乙醇,收率99%,纯度为99%,ee值为97%。
实施例8:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI3(18.6mg,0.024mmol),金属[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得120mg产物(S)-1-苯-1-乙醇,收率98%,纯度为98%,ee值为93%。
实施例9:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI5(21.3mg,0.024mmol),金属前体[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得121mg产物(S)-1-苯-1-乙醇,收率99%,纯度为99%,ee值为98%。
实施例10:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI8(18.0mg,0.024mmol),金属前体[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得116mg产物(S)-1-苯-1-乙醇,收率95%,纯度为98%,ee值为93%。
实施例11:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI9(22.0mg,0.024mmol),金属前体[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得116mg产物(S)-1-苯-1-乙醇,收率91%,纯度为98%,ee值为84%。
实施例12:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LII4(19.7mg,0.024mmol),金属前体[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),甲醇钠(2.7mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得121mg产物(S)-1-苯-1-乙醇,收率:97%,纯度为99%,ee值为94%。
实施例13:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI5(21.3mg,0.024mmol),金属前体[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),叔丁醇钠(4.8mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得121mg产物(S)-1-苯-1-乙醇,收率:99%,纯度为99%,ee值为99%。
实施例14:催化剂的制备及其催化苯乙酮的不对称氢化反应
(1)将配体LI5(21.3mg,0.024mmol),金属前体[Ir(COD)Cl]2(8mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入苯乙酮(120mg,1mmol),氢氧化钠(2.0mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得121mg产物(S)-1-苯-1-乙醇,收率:87%,纯度为98%,ee值为91%。
实施例15-21:催化剂的制备及其催化芳基乙酮的不对称氢化反应
(1)将配体LI5(21.3mg,0.024mmol),金属前体[Ir(COD)Cl]2(8mg,0.011mmol),加入反应瓶中,氩气氛围下加入异丙醇(2.2mL),25℃下搅拌反应0.5h,制得催化剂溶液。
(2)在高压釜中加入各种取代的芳基乙酮(1mmol),叔丁醇钠(4.8mg,0.05mmol),异丙醇(5mL),加入步骤(1)所制备的催化剂溶液(10μL,0.0001mmol),充入H2(3.0MPa),室温下反应12h。反应完毕释放氢气后,反应液经硅藻土过滤得对应的手性芳基乙醇类产物,产物的收率、纯度和ee值见表1。
反应式如下:
表1:实施例12~18的实验结果
Claims (5)
3.一种贵金属催化剂,其特征在于为由权利要求1所述的基于二茂铁骨架的手性氮氮膦三齿配体与过渡金属前体络合所得的配合物;过渡金属前体选自Pd(COD)Cl2、Pd(PPh3)4、PdCl2(PPh3)2、Pd(dba)2、Pd(OAc)2、PdCl2L2、[Rh(NBD)2]+BF4、[Rh(NBD)Cl]2、[Rh(COD)Cl]2、[Rh(COD)2]X、[Rh(acac)(CO)]2、Rh(ethylene)2(acac)、Rh(ethylene)2Cl2、RhCl(PPh3)3、Rh(CO)2Cl2、RuHX(L)2(diphosphine)、Ru(arene)X2(diphosphine)、Ru(aryl group)X2、Ru(RCO2)2(diphosphine)、Ru(methallyl)2(diphosphine)、Ru(aryl group)X2(PPh3)3、RuX2(L)2(diphosphine)、Ru(COD)(COT)、Ru(COD)(COT)X、RuX2(cymene)、Ru(aryl group)X2(diphosphine)、RuCl2(COD)、[Ru(COD)2]X、RuX2(diphosphine)、Ru(ArH)Cl2、Ru(COD)(methallyl)2、[Ir(NBD)2Cl]2、Ir(NBD)2)X、[Ir(COD)Cl]2或[Ir(COD)2]X中的任意一种;
过渡金属前体R为烷基、烷氧基或取代的烷基;aryl为芳基;X为阴离子,Ar为二(三氟甲基)苯或氟苯,L为溶剂分子,选自乙腈或苯甲腈。
4.根据权利要求3所述的贵金属催化剂,其特征在于X为BF4⁻、ClO4⁻、SbF6⁻、PF6⁻、CF3SO3⁻、B(Ar)4⁻;Ar为二(三氟甲基)苯或氟苯,L为溶剂分子,选自乙腈或苯甲腈。
5.一种根据权利要求3所述的贵金属催化剂在不对称氢化反应中的应用。
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