CN106565793A - 一种π‑烯丙基钯(II)配合物及其制备方法和应用 - Google Patents

一种π‑烯丙基钯(II)配合物及其制备方法和应用 Download PDF

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CN106565793A
CN106565793A CN201611030233.1A CN201611030233A CN106565793A CN 106565793 A CN106565793 A CN 106565793A CN 201611030233 A CN201611030233 A CN 201611030233A CN 106565793 A CN106565793 A CN 106565793A
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白涛
杨燕辉
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Abstract

本发明提供了一种新型π‑烯丙基钯(II)配合物及其制备方法和应用。本发明是通过[Xantphos]PdI(Ph)和砜基联烯发生插入反应后再与银盐反应生成离子型的π‑烯丙基钯(II)配合物，该配合物能用于催化联烯化合物的双官能团化反应，同时在联烯分子内引入C‑C和C‑O键。本发明的特点在于：该配合物能够实现对金属催化下联烯化合物的β‑H消除、聚合等竞争反应的抑制，使得反应单一化，并能实现反应的区域和立体选择性控制。

Description

一种π-烯丙基钯(II)配合物及其制备方法和应用
技术领域：
本发明涉及金属有机配合物，具体属于一种π-烯丙基钯(II)配合物及其制备方法，并将该配合物作为催化剂用于催化联烯的双官能团化反应。
背景技术：
多取代的烯丙醇结构单元作为一种重要的有机单元经常出现在天然产物中，在过渡金属催化下通过烯丙基化合物的亲核取代反应是制备烯丙醇的有效方法，例如Tsuji–Trost反应，此类方法需要用到毒性较大的烯丙基卤代物，这样无疑增加了反应的步骤与制备难度。那么能否不通过制备烯丙基卤化物直接合成烯丙醇类化合物就成为了本研究的主要目标。含有三个相邻共轭碳原子的联烯作为一种重要的有机小分子，在金属催化作用下能用于制备烯丙基化合物，一般来说在同一个联烯分子内进行两次的C-C键偶联较为常见，那么能否同时构建不同类型的偶联反应就成为了本项研究的方式，本发明通过配体对金属钯Pd(II)电性的调控实现了烯丙基化合物的羟基化，即在生成C-C键的同时生成C-O键，得到的多取代烯丙醇能进一步衍生化为烯丙醇酯、烯丙基卤等烯丙基类化合物，此类化合物也可以作为重要的合成砌块用于复杂分子的构建。
发明内容：
本发明的目的在于提供一种π-烯丙基钯(II)配合物及其制备方法，并将其用于催化联烯化合物的双官能团化反应。
利用有机硼酸作为产生羟基化合物的媒介在文献中的报道很少，本发明的核心内容正是基于此，利用芳基硼酸向联烯化合物导入羟基官能团最终得到多取代的烯丙醇类化合物，实现在联烯的同一个碳碳双键的两端碳原子上分别引入不同性质的亲电基团和亲核基团。对空气稳定的配合物A可以有效的催化此类反应，相信这样的化学转化在未来的药物合成领域会有广泛用途。
本发明提供的一种π-烯丙基钯(II)配合物，结构式如下：
式中R＝烷基或芳基；Ar＝芳基；R’＝砜基、膦酸酯、膦氧、酯基、烷基或芳基；X＝BF4、SbF6、OTf或PF6。
本发明提供的一种π-烯丙基钯(II)配合物的制备方法，其反应式为：
式中R＝烷基或芳基；Ar＝芳基；R’＝砜基、膦酸酯、膦氧、酯基、烷基或芳基；X＝BF4、SbF6、OTf或PF6；
该方法包括如下步骤：
1.在手套箱中，将30mg(Xantphos)PdPhI配合物溶于二氯甲烷(3mL)中；
2.在手套箱中，将1.2当量的砜基联烯(7mg)溶于二氯甲烷(1mL)中；
3.在手套箱中，将步骤2中的砜基联烯溶液滴加到步骤1中的(Xantphos)PdPhI溶液中，搅拌10-15小时，反应由开始时的黄色变为深红色；
4.在反应液中直接加入1.0当量的四氟硼酸银固体，继续在室温下搅拌5小时直至反应液变为黄绿色，并伴有棕色沉淀析出，过滤除掉沉淀，抽干二氯甲烷溶剂后得到黄绿色固体，然后加入乙醚(3mL×3次)洗涤得到的固体，产物经过真空干燥后为黄色固体。经过检测该催化剂对干燥的空气是稳定的。
附图说明
图1、图2、图3和图4分别为实施例1配合物A的X-射线衍射图、核磁氢谱图、碳谱图和磷谱图；
图5为实施例2产物4a的核磁氢谱图和碳谱图；
图6为实施例3产物4b的核磁氢谱图和碳谱图；
图7为实施例4产物4c的核磁氢谱图和碳谱图；
图8为实施例5产物4d的核磁氢谱图和碳谱图；
图9为实施例6产物4e的核磁氢谱图和碳谱图；
图10为实施例7产物4f的核磁氢谱图和碳谱图；
图11为实施例8产物4g的核磁氢谱图和碳谱图；
图12为实施例9产物4h的核磁氢谱图和碳谱图；
图13为实施例10产物4i的核磁氢谱图和碳谱图；
图14为实施例11产物4j的核磁氢谱图和碳谱图；
图15为实施例12产物4k的核磁氢谱图和碳谱图；
图16为实施例13产物4l的核磁氢谱图和碳谱图；
图17为实施例14产物4m的核磁氢谱图和碳谱图；
图18为实施例15产物5a的核磁氢谱图和碳谱图；
具体实施方式
实施例1：配合物A的制备：
⑴在手套箱中(H2O<0.1ppm；O2<0.1ppm)，将0.033mmol[(Xantphos)PdPhI]配合物溶于3ml二氯甲烷中得亮黄色溶液；
⑵在手套箱中，将砜基联烯(7mg，1.2当量)溶于1ml二氯甲烷中得无色溶液；
⑶在手套箱中，将步骤⑵中的砜基联烯溶液在搅拌下滴加到步骤⑴中的(Xantphos)-PdPhI溶液中，溶液由亮黄色变为深红色，继续溶液搅拌10小时；
⑷在反应液中直接加入6.4mg的四氟硼酸银固体(6.4mg，1.0当量)，继续在室温下搅拌5小时直至反应液变为黄绿色，并伴有棕色沉淀析出，过滤除掉沉淀，抽干二氯甲烷溶剂后得到黄绿色固体，然后加入乙醚(3mL×3次)洗涤得到的固体，产物经过真空干燥后为黄色固体(25mg，产率：70％)。
黄色固体(25mg,70％)：1H NMR(600MHz,CDCl3)δ7.69(d,1H,J(PH)＝12Hz),7.64(d,1H,J(PH)＝12Hz),7.60-7.49(m,8H),7.48-7.43(m,7H),7.42-7.34(m,5H),7.31(t,2H,J＝6Hz),7.23-7.14(m,6H),6.92-6.85(m,4H),6.65(t,2H,J＝6Hz),5.32(d,1H,J＝6Hz),4.98(br s,1H),3.97(br s,1H),1.81(s,3H),1.44(s,3H)；13C NMR(150MHz,CDCl3)δ155.26(d,J(PC)＝7.6Hz),154.98(d,J(PC)＝7.6Hz),140.67(d,J(PC)＝3.0Hz),134.86(d,J(PC)＝3.0Hz),134.66,134.56(d,J(PC)＝3.0Hz),133.57(d,J(PC)＝13.6Hz),132.96(d,J(PC)＝13.6Hz),132.8(d,J(PC)＝9.0Hz),132.73,132.62(d,J(PC)＝24.1Hz),132.81(d,J(PC)＝12.1Hz),132.01,131.73,131.31(d,J(PC)＝3.0Hz),130.13(d,J(PC)＝9.0Hz),129.80(d,J(PC)＝12.1Hz),129.65(d,J(PC)＝9.0Hz),129.66,129.15,129.00(d,J(PC)＝7.6Hz),128.93(d,J(PC)＝7.6Hz),127.92(d,J(PC)＝43.8Hz),126.96,126.67(d,J(PC)＝43.8Hz),125.72(d,J(PC)＝7.6Hz),125.39(d,J(PC)＝7.6Hz),118.16(d,J(PC)＝45.3Hz),115.79(d,J(PC)＝45.3Hz),90.61(d,J(PC)＝40.77Hz),77.66(t,J(PC)＝33.22Hz),36.39,30.85,25.11；31P NMR(243MHz,CDCl3)δ5.03(d,J(PP)＝29.2Hz),-0.15(d,J(PP)＝29.2Hz).
实施例2：用配合物A催化砜基联烯的苯基-羟基化反应，为了分离的方便，再将双官能团化产物在“咪唑/叔丁基二甲基氯硅烷”的作用下硅醚化，得产物4a，两步的总产率(下同)为80％,催化剂的负载量为2.5mol％。
无色油状物：1H NMR(600MHz,C6D6)δ7.93(2H,s),7.11-6.95(8H,m),6.41(1H,s),5.27(2H,s),0.79(9H,s),0.03(6H,s)；13C NMR(150MHz,C6D6)δ155.69,143.27,138.14,133.38,129.80,129.64,128.95,128.70,128.43,127.93,58.89,26.18,18.60,-4.87；IR(film,cm-1):2924,1470,1303,1287,1174,1144,1082,837；HRMS(ESI+):Calcd forC21H29O3SSi[M+H]+:389.16012；Found:389.15999.
实施例3：用配合物A催化砜基联烯的对甲基苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4b，产率为57％。
白色固体(46mg,57％)：Melting point 64-66℃,1H NMR(600MHz,C6D6)δ7.97-7.92(2H,m),7.09(2H,d,J＝6Hz),6.98-6.93(3H,m),6.85(2H,d,J＝6Hz),6.49(1H,s),5.30(2H,s),2.03(3H,s),0.83(9H,s),0.07(6H,s)；13C NMR(150MHz,C6D6)δ155.49,143.48,139.99,135.26,133.28,129.61,129.48,128.68,128.43,127.90,58.81,26.24,21.46,18.65,-4.82；IR(film,cm-1):2929,1316,1140,1106,812,788,688；HRMS(ESI+):Calcd for C22H31O3SSi+[M+H]+:403.17577；Found:403.17579.
实施例4：用配合物A催化砜基联烯的对氟苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4c，产率为54％。
白色固体(44mg,54％)：Melting point 82-83℃,1H NMR(600MHz,C6D6)δ7.95-7.91(2H,m),6.99-6.93(3H,m),6.89-6.84(2H,m),6.67-6.62(2H,m),6.30(1H,s),5.20(2H,s),0.79(9H,s),0.02(6H,s)；13C NMR(150MHz,C6D6)δ164.90,163.25,154.38,143.20,133.95(d,J＝3Hz),133.44,130.42(d,J＝7.5Hz),129.65,128.84,128.68,127.93,115.67(d,J＝7.5Hz),58.76,26.14,18.56,-4.90；19F NMR(564.6MHz,C6D6)δ-111.47；IR(film,cm-1):2850,1599,1507,1305,1163,1142,829,772；HRMS(ESI+):Calcd for C21H28FO3SSi+[M+H]+:407.15070；Found:407.15066.
实施例5：用配合物A催化砜基联烯的对氯苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4d，产率为53％。
白色固体(45mg,53％)：Melting point 112-113℃；1H NMR(600MHz,C6D6)δ7.94-7.90(2H,m),6.99-6.94(5H,m),6.81(2H,d,J＝6Hz),6.30(1H,s),5.18(2H,s),0.79(9H,s),0.02(6H,s)；13C NMR(150MHz,C6D6)δ154.20,143.06,136.43,135.93,133.51,129.80,129.68,129.24,128.91,128.68,127.95,58.69,26.14,18.64,-4.90；IR(film,cm-1):2855,1597,1489,1142,1082,809,687；HRMS(ESI+):Calcd for C21H28ClO3SSi+[M+H]+:423.12114[Cl35],425.11819[Cl37]；Found:423.12084[Cl35],425.11727[Cl37].
实施例6：用配合物A催化砜基联烯的对溴苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4e，产率为52％。
白色固体(48mg,52％)：Melting point 83-85℃；1H NMR(600MHz,C6D6)δ7.92-7.90(2H,m),7.13(2H,d,J＝6Hz),6.95-6.93(3H,m),6.73(2H,d,J＝6Hz),6.29(1H,s),5.18(2H,s),0.79(9H,s),0.01(6H,s)；13C NMR(150MHz,C6D6)δ154.26,143.05,136.90,133.49,131.89,130.01,129.66,129.25,128.68,127.95,124.24,58.66,26.07,18.58,-4.91；IR(film,cm-1):2855,1598,1485,1141,1125,853,790；HRMS(ESI+):Calcd forC21H28BrO3SSi+[M+H]+:467.07063[Br79],469.06858[Br81]；Found:467.07039[Br79],469.06806[Br81].
实施例7：用配合物A催化砜基联烯的对叔丁基苯基－羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4f，产率为73％。
无色油状物(65mg,73％)：1H NMR(600MHz,C6D6)δ7.98-7.95(2H,m),7.18-7.12(4H,m),7.01-6.97(3H,m),6.51(1H,s),5.30(2H,s),1.15(9H,s),0.82(9H,s),0.06(6H,s)；13C NMR(150MHz,C6D6)δ155.47,153.13,143.47,135.37,133.32,129.63,128.68,128.30,127.92,125.72,58.92,34.95,31.53,26.22,18.66,-4.81；IR(neat,cm-1):2961,1598,1300,1148,1112,857,755；HRMS(ESI+):Calcd for C25H37O3SSi+[M+H]+:445.22272；Found:445.22280.
实施例8：用配合物A催化砜基联烯的间甲基苯基－羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4g，产率为59％。
无色油状物(48mg,59％)：1H NMR(600MHz,C6D6)δ7.96-7.93(2H,m),7.04-6.94(6H,m),6,90-6.86(1H,m),6.48(1H,s),5.28(2H,s),2.02(3H,s),0.81(9H,s),0.04(6H,s)；13C NMR(150MHz,C6D6)δ155.84,143.35,138.21,138.19,133.37,130.62,129.63,129.11,128.86,128.69,127.93,125.60,59.00,26.20,21.54,18.63,-4.86；IR(neat,cm-1):2855,1599,1305,1254,1147,1083,834,811；HRMS(ESI+):Calcd for C22H31O3SSi+[M+H]+:403.17577；Found:403.17595.
实施例9：用配合物A催化砜基联烯的间氯苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4h，产率为50％。
无色油状物(42mg,50％)：1H NMR(600MHz,C6D6)δ7.90(2H,d,J＝6Hz),7.25(1H,s),7.01-6.93(4H,m),6.76(1H,d,J＝12Hz),6.68(1H,t,J＝6Hz),6.30(1H,s),5.15(2H,s),0.79(9H,s),0.00(6H,s)；13C NMR(150MHz,C6D6)δ154.07,142.90,139.96,134.71,133.54,129.98,129.82,129.68,128.71,127.96,126.44,58.85,26.13,18.54,-4.97；IR(neat,cm-1):2855,1471,1446,1306,1254,1147,1083,775,686；HRMS(ESI+):Calcd forC21H28ClO3SSi+[M+H]+:423.12115；Found:423.12107.
实施例10：用配合物A催化砜基联烯的间甲氧基苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4i，产率为50％。
无色油状物(42mg,50％)：1H NMR(600MHz,C6D6)δ7.93(2H,d,J＝6Hz),6.98-6.91(5H,m),6.75(1H,d,J＝6Hz),6.70(1H,d,J＝6Hz),6.50(1H,s),5.26(2H,s),3.26(3H,s),0.82(9H,s),0.05(6H,s)；13C NMR(150MHz,C6D6)δ160.32,155.43,143.22,139.78,133.37,129.82,129.63,129.25,127.94,120.70,115.69,114.04,59.05,55.17,26.23,18.56,-4.86；IR(neat,cm-1):2928,1575,1485,1289,1170,835,776；HRMS(ESI+):Calcd forC22H31O4SSi+[M+H]+:419.17068；Found:419.17075.
实施例11：用配合物A催化砜基联烯的3，5-二甲基苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4j，产率为56％。
无色油状物(47mg,56％)：1H NMR(600MHz,C6D6)δ7.98-7.94(2H,m),6.96(3H,s),6.88(2H,s),6.71(1H,s),6.54(1H,s),5.30(2H,s),2.04(6H,s),0.77(9H,s),0.05(6H,s)；13CNMR(150MHz,C6D6)δ155.99,143.45,138.23,138.08,133.29,131.59,129.62,128.74,127.92,126.31,59.11,26.21,21.48,18.65,-4.85；IR(neat,cm-1):2885,1595,1306,1254,1147,1101,1083,835,776；HRMS(ESI+):Calcd for C23H33O3SSi+[M+H]+:417.19142；Found:417.19104.
实施例12：用配合物A催化对甲基砜基联烯的苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4k，产率为66％。
白色固体(53mg,66％)：Melting point 92-93℃；1H NMR(600MHz,C6D6)δ7.88(2H,d,J＝6Hz),7.12(2H,d,J＝6Hz),7.05-6.97(3H,m),6.83(2H,d,J＝6Hz),6.46(1H,s),5.30(2H,s),1.90(3H,s),0.80(9H,s),0.04(6H,s)；13C NMR(150MHz,C6D6)δ155.14,144.34,140.46,138.23,130.34,129.74,129.38,128.71,128.43,128.08,58.88,26.20,21.54,18.61,-4.85；IR(neat,cm-1):2854,1598,1313,1299,1139,1078,809,781；HRMS(ESI+):Calcd for C22H31O3SSi+[M+H]+:403.17577；Found:403.17565.
实施例13：用配合物A催化对甲氧基砜基联烯的苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物4l，产率为57％。
白色固体(48mg,57％)：Melting point 56-58℃；1H NMR(600MHz,C6D6)δ7.91(2H,d,J＝6Hz),7.14(2H,d,J＝12Hz),7.05-6.98(3H,m),6.56(2H,d,J＝12Hz),6.48(1H,s),5.33(2H,s),3.11(3H,s),0.81(9H,s),0.07(6H,s)；13C NMR(150MHz,C6D6)δ163.94,154.55,138.55,134.97,130.25,129.76,129.67,128.70,128.44,114.97,58.89,55.40,26.21,18.62,-4.82；IR(neat,cm-1):2928,1594,1497,1257,1141,1084,831,776；HRMS(ESI+):Calcd for C22H31O4SSi+[M+H]+:419.17068；Found:419.17058.
实施例14：用配合物A催化对溴砜基联烯的苯基-羟基化反应，再将双官能团化产物烯丙醇硅醚化，得产物6m，产率为35％。
白色固体(33mg,35％)：Melting point 52-53℃；1H NMR(600MHz,C6D6)δ7.56(2H,d,J＝6Hz),7.11(2H,d,J＝6Hz),7.06(2H,d,J＝6Hz),7.03-6.98(3H,m),6.31(1H,s),5.20(2H,s),0.79(9H,s),0.02(6H,s)；13C NMR(150MHz,C6D6)δ156.15,142.03,138.13,132.91,129.98,129.45,128.77,128.68,58.85,26.15,18.59,-4.90；IR(neat,cm-1):2932,1601,1574,1306,1146,1084,1009；HRMS(ESI+):Calcd for C21H28BrO3SSi+[M+H]+:467.07063[Br79],469.06858[Br81]；Found:467.07063[Br79],469.06832[Br81].
实施例2-14中，烯丙基硅醚化合物4b-4m均可脱除相应的硅保护基变为相应的烯丙醇化合物(如实施例15)。
实施例15：实施例2中从烯丙基硅醚化合物4a出发能够得到相应的烯丙醇化合物5a，水解产率为96％。
白色固体：Melting point:82-83℃；1H NMR(600MHz,C6D6)δ7.86-7.82(2H,m),7.05-7.03(2H,m),7.01-6.88(6H,m),6.40(1H,s),4.76(2H,d,J＝6Hz),2.98(1H,br s)；13CNMR(150MHz,C6D6)δ156.04,142.71,138.87,133.52,130.09,130.07,129.69,129.13,128.68,127.92,127.63,60.29；IR(neat,cm-1):3500,1597,1443,1301,1174,1082,1033,836,771；HRMS(ESI+):Calcd for C15H15O3S+[M+H]+:275.07364；Found:275.07338.

Claims (3)

1.一种π-烯丙基钯(II)配合物，其特征在于结构式为：
式中R＝烷基或芳基；Ar＝芳基；R’＝砜基、膦酸酯、膦氧、酯基、烷基或芳基；X＝BF4、SbF6、OTf或PF6。
2.如权利要求1所述的π-烯丙基钯(II)配合物的制备方法，其特征在于反应式为：
式中R＝烷基或芳基；Ar＝芳基；R’＝砜基、膦酸酯、膦氧、酯基、烷基或芳基；X＝BF4、SbF6、OTf或PF6；
3.如权利要求1所述的π-烯丙基钯(II)配合物作为催化剂在联烯化合物双官能团化反应中的应用。
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012119927A1 (de) * 2011-03-08 2012-09-13 Basf Se Verfahren zur herstellung von primären aminen durch homogen-katalysierte alkoholaminierung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012119927A1 (de) * 2011-03-08 2012-09-13 Basf Se Verfahren zur herstellung von primären aminen durch homogen-katalysierte alkoholaminierung

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* Cited by examiner, † Cited by third party
Title
HU等，: "Palladium-Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by C_N Bond Activation", 《ANGEW. CHEM. INT. ED.》 *

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