CN104744519B - 含吡啶甲基的扩环氮杂环卡宾钯化合物 - Google Patents

含吡啶甲基的扩环氮杂环卡宾钯化合物 Download PDF

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CN104744519B
CN104744519B CN201510107498.6A CN201510107498A CN104744519B CN 104744519 B CN104744519 B CN 104744519B CN 201510107498 A CN201510107498 A CN 201510107498A CN 104744519 B CN104744519 B CN 104744519B
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ring expansion
heterocyclic carbine
palladium compound
picolyl
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杨亮茹
买文鹏
毛璞
肖咏梅
袁金伟
屈凌波
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Henan University of Technology
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Abstract

本发明属于有机化合物领域，涉及钳形扩环氮杂环卡宾钯化合物。该化合物具有如下结构：

Description

含吡啶甲基的扩环氮杂环卡宾钯化合物
技术领域
本发明属于有机化合物领域，涉及钳形扩环氮杂环卡宾钯化合物及其在催化C-N偶联反应中的应用。
背景技术
氮杂环卡宾(N-Heterocyclic Carbenes,NHCs)及其金属化合物多用于金属有机化学、配位化学、均相催化、材料化学以及药物化学研究领域。目前研究多集中在五元氮杂环卡宾(五元-NHCs)及其金属化合物，包括咪唑衍生的经典型咪唑-2-卡宾金属化合物、咪唑啉-2-卡宾金属化合物(A-D)和Crabtree教授课题组首次报道的以咪唑-4-卡宾为代表的非经典型卡宾金属化合物(E-F)。
咪唑衍生的五元-NHCs-金属化合物
三齿的钳形氮杂环卡宾配体，即配体中的卡宾碳、Ν上所连取代基中具有配位功能的杂原子，与同一金属中心配位，形成具有环状结构的配合物。此外，氮杂环卡宾配体本身还具有较强的σ-配位能力，因而三齿的钳形五元氮杂环卡宾金属化合物通常情况下对空气、水分以及热的稳定性增强，有利于其制备和应用，在均相催化方面取得了非常广泛的应用。例如，三齿配位的PCP、NCN、CCC、CNC钳形五元-氮杂环卡宾钯化合物被广泛应用于Heck、Suzuki等C-C偶联反应(参考文献(a)Liao,C.–Y.；Chan,K.–T.；Zeng,J.–Y.；Hu,C.–H.；Tu,C.–Y.；Lee,H.M.Organometallics 2007,26,1692.(b)Hahn,F.E.；Jahnke,M.C.；Pape,T.Organometallics 2006,25,5927.(c)Lee,H.M.；Zeng,J.Y.；Hu,C.–H.；Lee,M.–T.Inorg.Chem.2004,43,6822.(d)Tsoureas,N.；Danopoulos,A.A.；Tulloch,A.A.D.；Light,M.E.Organometallics 2003,22,4750.(e)Herrmann,W.A.；V.P.W.；C.W.K.；Grosche,M.；Reisinger,C.–P.；Weskamp,T.J.Organomet.Chem.2001,617-618,616.(f)Yang,C.；Lee,H.M.；Nolan,S.P.Org.Lett.2001,3,1511.)。
钳形NHC-Pd化合物催化的C-C偶联反应
杂环上原子数目大于五的NHCs被称为扩环氮杂环卡宾(Ring-Expanded NHCs,RE-NHCs)，与五元-NHCs相比，六元-、七元-等RE-NHCs表现出相当不同的性质，尤其是显著增强的碱性/亲核性和空间效应，因而相应金属化合物的结构特征、催化活性和选择性也明显不同。由于扩环氮杂环卡宾的σ-供电子能力增强，N-Ccarbene-N键角变大，R-N-Ccarbene键角变小，促使N上取代基更加靠近金属中心，使位阻效应增大，从而提高催化剂的活性和稳定性。已报道的扩环氮杂环卡宾金属化合物的结构如下所示(参考文献(a)Collins,L.R.；Rookes,T.M.；Mahon,M.F.；Riddlestone,I.M.；Whittlesey,M.K.Organometallics 2014,33,5882.(b)Dunsford,J.J.；Cavell,K.J.；Kariuki,B.M.Organometallics 2012,31,4118.(c)Park,J.K.；Lackey,H.H.；Ondrusek,B.A.；McQuade,D.T.J.Am.Chem.Soc.2011,133,2410.(d)Armstrong,R.；Ecott,C.；Mas-Marzá,E.；Page,M.J.；Mahon,M.F.；Whittlesey,M.K.Organometallics 2010,29,991.(e)Scarborough,C.C.；Grady,M.J.W.；Guzei,I.A.；Gandhi,B.A.；Bunel,E.E.；Stahl,S.S.Angew.Chem.,Int.Ed.2005,44,5269.
文献报道的部分六元-、七元-、等RE-NHCs-金属化合物
目前，在RE-NHCs及其金属化合物的合成及性能的文献报道中，氮杂环卡宾中的卡宾碳与金属配位，形成单齿配位的简单络合物，催化效果不太理想。探索新的钳形扩环氮杂环卡宾金属催化剂，有利于钯催化的C-N偶联反应芳胺类化合物的合成。目前三齿配位的钳形扩环氮杂环卡宾金属化合物未见报道。
发明内容
本发明的目的在于提供催化效果好的三齿配位钳形扩环氮杂环卡宾钯化合物。
本发明所述的钳形扩环氮杂环卡宾钯化合物具有以下通式：
R同时相同或不同；X同时相同或不同。
优选结构如下化合物：
上述化合物合成路线如下：
本发明所述的钳形的扩环氮杂环卡宾钯化合物的合成方法通过如下步骤实现：
(1)1,3-丙二胺衍生物与2-吡啶甲醛衍生物以1:2摩尔比，在甲醇中，依次经脱水、还原得双取代1,3-丙二胺衍生物；进一步与等摩尔量的甲醛水溶液在甲醇中发生关环反应，生成六氢嘧啶衍生物；
(2)六氢嘧啶衍生物与NBS以1:1摩尔比，在乙二醇二甲醚反应脱氢，生成四氢嘧啶溴鎓盐衍生物后，与1.5摩尔量的六氟磷酸铵在乙醇中发生阴离子交换，生成四氢嘧啶六氟磷酸鎓盐；
(3)四氢嘧啶六氟磷酸鎓盐与氯化钯以1:0.5-2摩尔比、在有机溶剂中、在碱存在下，在50～200℃温度下、反应5～25小时，减压除去溶剂后，过柱分离得到钳形的扩环氮杂环卡宾钯化合物。
本发明所述的1,3丙二胺衍生物为1,3-丙二胺、2,2-二甲基-1,3-丙二胺；所述的2-吡啶甲醛衍生物为2-吡啶甲醛，5-溴-2-吡啶甲醛、6-溴-2-吡啶甲醛。
本发明所述的有机溶剂为四氢呋喃、甲苯、1,4-二氧六环、吡啶、N,N-二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、乙二醇二甲醚、二甲基亚砜。
本发明所述的碱为双(三甲基硅烷基)氨基钠、双(三甲基硅烷基)氨基钾、叔丁醇钠、叔丁醇钾、叔戊醇钠、叔戊醇钾。
本发明合成的钳形扩环氮杂环卡宾钯化合物具有独特的结构特点，在微波辐射下对溴苯、杂环卤代芳烃与胺的C-N偶联反应表现出高效的催化性能，芳胺常见于药物分子及天然产物中，也是许多新型功能材料的重要结构单元。钯催化的C-N偶联反应是合成芳胺类化合物的一种重要方法。本发明化合物为C-N偶联反应提供一类新型的金属催化剂，用于催化C-N偶联反应时，反应时间短，催化剂用量少、使用廉价易得的碱、反应溶剂无需处理、操作简单、催化产率高。
催化C-N偶联反应采用以下步骤：将本发明钳形扩环氮杂环卡宾钯化合物催化剂、碱、卤代芳烃、胺加入到溶剂中，在微波辐射下于50～100℃反应10～40分钟后，降至室温，减压除去溶剂，柱色谱分离得到纯品。
具体实施方式
以下结合较佳实例，对本发明进行进一步描述，但本发明的保护范围并不仅限于此：
实施例1
在100mL圆底烧瓶中，将吡啶-2-甲醛(30mmol,3.21g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合，室温反应5.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得残留黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得1,3-二(2-吡啶甲基)六氢嘧啶(3.50g，产率87％)。
在100mL圆底烧瓶中，将1,3-二(2-吡啶甲基)六氢嘧啶(5mmol,1.34g)溶于30mL乙二醇二甲醚(DME)，向其中加入N-溴代丁二酰亚胺(NBS,5mmol,0.89g)，室温搅拌3小时后，抽滤,将淡黄色滤饼经二氯甲烷-***重结晶，得1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐纯品。将1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后，旋干溶剂，残留物用二氯甲烷-***重结晶，得四氢嘧啶六氟磷酸鎓盐纯品(1.75g，产率85％)。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，0.82g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(I)。无色固体(0.64g,58％).1H NMR(400MHz,DMSO-d6):δ9.00-8.98(m,2H,Py-H),8.22-8.18(m,2H,Py-H),7.88(d,J＝7.1Hz,2H,Py-H),7.67-7.63(m,2H,Py-H),5.30(d,J＝15.1Hz,2H,picolyl-CH2),4.80(d,J＝15.3Hz,2H,picolyl-CH2),3.58-3.48(m,4H,pyrimidine-CH2),1.92(t,J＝5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.9,154.8,154.0,141.4,125.6,125.2,61.6,47.5,20.8ppm.Anal Cacld for C16H18ClF6N4PPd(551.99):C,34.74；H,3.28；N,10.13.Found:C,34.56；H,3.02；N,9.89.
实施例2
将吡啶-2-甲醛(30mmol,3.21g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合，室温反应7.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时。停止反应，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，再向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得3,3-二甲基-1,3-二(2-吡啶甲基)六氢嘧啶(3.96g，产率89％)。
将3,3-二甲基-1,3-二(2-吡啶甲基)六氢嘧啶(5mmol,1.48g)溶于30mLDME，再向其中加入NBS(5mmol,0.89g)，室温搅拌3小时后，抽滤得淡黄色粉末，经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干，再用CH2Cl2溶解、过滤，将滤液旋蒸，残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(1.89g，产率86％)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，0.88g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(II)。淡黄色固体(0.70g,60％).1H NMR(400MHz,DMSO-d6):δ9.01(d,J＝4.9Hz,2H,Py-H),8.23-8.19(m,2H,Py-H),7.86(d,J＝7.4Hz,2H,Py-H),7.68-7.65(m,2H,Py-H),5.38(d,J＝15.1Hz,2H,picolyl-CH2),4.77(d,J＝15.2Hz,2H,picolyl-CH2),3.28(d,J＝3.2Hz,4H,pyrimidine-CH2),0.79(s,6H,CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.0,154.9,154.0,141.5,125.5,125.2,61.6,58.7,28.1,23.5ppm；Anal Cacld forC18H22ClF6N4PPd(580.02):C,37.20；H,3.82；N,9.64；Found:C,36.93；H,3.87；N,9.49.
实施例3
将5-溴吡啶-2-甲醛(30mmol,5.58g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合，室温反应5.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时。停止反应，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，再向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5.30g，产率83％)。
将1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.13g)溶于30mL DME，再向其中加入NBS(5mmol,0.89g)，室温搅拌3小时后，抽滤得淡黄色粉末，经二氯甲烷-***重结晶得1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将1,3-二(5-溴2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干，再用CH2Cl2溶解、过滤，将滤液旋蒸，残留物用二氯甲烷-***重结晶得1,3-二(5-溴2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.42g，产率85％)。
在Schlenk瓶中加入1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，1.14g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(III)。浅黄色固体(0.75g,53％).1H NMR(400MHz,DMSO-d6):δ9.10-9.08(s,2H,Py-H),8.32-8.28(d,J＝7.1Hz,,2H,Py-H),7.98(d,J＝7.1Hz,2H,Py-H),5.35(d,J＝15.1Hz,2H,picolyl-CH2),4.86(d,J＝15.2Hz,2H,picolyl-CH2),3.63-3.54(m,4H,pyrimidine-CH2),1.97(t,J＝5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.8,154.3,153.6,141.0,125.1,124.7,61.5,47.3,20.6ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C,27.03；H,2.27；N,7.88.Found:C,27.28；H,2.09；N,7.70.
实施例4
将5-溴吡啶-2-甲醛(30mmol,5.58g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合，室温反应7.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时。停止反应，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，再向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5.52g，产率81％)。
将3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.27g)溶于30mLDME，再向其中加入NBS(5mmol,0.89g)，室温搅拌3小时后，抽滤得淡黄色粉末，经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干，再用CH2Cl2溶解、过滤，将滤液旋蒸，残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.51g，产率84％)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(5-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，1.20g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(IV)。浅黄色固体(0.81g,55％).1H NMR(400MHz,DMSO-d6):δ9.11(s,2H,Py-H),8.32-8.29(d,J＝7.5Hz,,2H,Py-H),7.96(d,J＝7.5Hz,2H,Py-H),5.43(d,J＝15.2Hz,2H,picolyl-CH2),4.82(d,J＝15.2Hz,2H,picolyl-CH2),3.32(d,J＝3.2Hz,4H,pyrimidine-CH2),0.84(s,6H,CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.1,154.4,153.5,141.0,125.1,124.7,61.4,58.5,27.9,23.3ppm；Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25；H,2.73；N,7.58；Found:C,29.10；H,2.87；N,7.40.
实施例5
将6-溴吡啶-2-甲醛(30mmol,5.58g)和1,3-丙二胺(15mmol,1.11g)在30mL甲醇中混合，室温反应5.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时。停止反应，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，再向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5.25g，产率82％)。
将1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.13g)溶于30mL DME，再向其中加入NBS(5mmol,0.89g)，室温搅拌3小时后，抽滤得淡黄色粉末，经二氯甲烷-***重结晶得1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将1,3-二(6-溴2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干，再用CH2Cl2溶解、过滤，将滤液旋蒸，残留物用二氯甲烷-***重结晶得1,3-二(6-溴2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.36g，产率83％)。
在Schlenk瓶中加入1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，1.14g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(V)。浅黄色固体(0.78g,55％).1H NMR(400MHz,DMSO-d6):δ8.27-8.23(m,2H,Py-H),7.93(d,J＝7.2Hz,2H,Py-H),7.72-7.68(m,2H,Py-H),5.33(d,J＝15.2Hz,2H,picolyl-CH2),4.83(d,J＝15.3Hz,2H,picolyl-CH2),3.62-3.53(m,4H,pyrimidine-CH2),1.95(t,J＝5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ175.0,155.3,154.4,141.9,126.0,125.6,61.9,47.8,21.0ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C,27.03；H,2.27；N,7.88.Found:C,27.30；H,2.08；N,7.65.
实施例6
将6-溴吡啶-2-甲醛(30mmol,5.58g)和2,2-二甲基-1,3-丙二胺(15mmol,1.53g)在30mL甲醇中混合，室温反应7.0小时后，冰水浴搅拌下缓慢加入NaBH4(120mmol,4.54g)，慢慢升温至70℃反应5小时。停止反应，冷却至室温，旋干反应液。再用50mL CH2Cl2溶解、过滤，滤液旋干，得黄色油状黏稠物。将上述黄色油状黏稠物溶于30mL甲醇后，再向其中加入等摩尔量甲醛水溶液，室温搅拌3小时后，减压除去溶剂，柱层析分离纯化得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5.23g，产率77％)。
将3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)六氢嘧啶(5mmol,2.27g)溶于30mLDME，再向其中加入NBS(5mmol,0.89g)，室温搅拌3小时后，抽滤得淡黄色粉末，经二氯甲烷-***重结晶得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐。将3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶溴鎓盐和1.5摩尔量的六氟磷酸铵在乙醇中室温搅拌5小时后蒸干，再用CH2Cl2溶解、过滤，将滤液旋蒸，残留物用二氯甲烷-***重结晶得3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐纯品(2.60g，产率87％)。
在Schlenk瓶中加入3,3-二甲基-1,3-二(6-溴-2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，1.20g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(VI)。浅黄色固体(0.75g,51％).1H NMR(400MHz,DMSO-d6):δ8.28-8.24(m,2H,Py-H),7.90(d,J＝7.3Hz,2H,Py-H),7.73-7.70(m,2H,Py-H),5.40(d,J＝15.1Hz,2H,picolyl-CH2),4.81(d,J＝15.2Hz,2H,picolyl-CH2),3.30(d,J＝3.1Hz,4H,pyrimidine-CH2),0.80(s,6H,CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.1,155.4,154.5,141.9,125.9,125.7,62.0,59.0,28.3,23.8ppm；Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25；H,2.73；N,7.58；Found:C,28.99；H,2.80；N,7.43.
实施例7
其它步骤同上。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，0.82g)和PdCl2(2mmol，0.35g)，氩气保护下加入NaN(SiMe3)2(2.1mmol)和甲苯(8mL)，油浴120℃搅拌20h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(I)。数据见实施实例1。
实施例8：
其它步骤同上。
在Schlenk瓶中加入1,3-二(2-吡啶甲基)四氢嘧啶六氟磷酸鎓盐(2mmol，0.82g)和PdCl2(2mmol，0.35g)，氩气保护下加入KN(SiMe3)2(2.1mmol)和吡啶(6mL)，油浴140℃搅拌12h。反应结束后，将反应液冷却至室温，过滤，滤液经柱层析分离纯化(梯度洗脱，展开剂：正己烷/二氯甲烷＝1/10～1/20)，得钳形扩环氮杂环卡宾钯化合物(I)。数据见实施例1。
应用例：
部分C-N偶联催化反应实例：
将卤代芳烃(1.0mmol)、胺(3.0mmol)、碱(2.0mmol)、本发明钳形扩环氮杂环卡宾钯化合物催化剂(0.01mmol)加入到溶剂中，微波辐射下于50～100℃反应10～40分钟后，降至室温，减压除去溶剂，柱色谱分离得到纯品。
部分催化反应结果如下表：
以上数据显示了所合成的钳形扩环氮杂环卡宾钯化合物对C-N偶联反应具有很好的催化效果。而C-N偶联反应在有机合成、药物研发以及功能性材料开发等具有重要的地位，本发明合成的钳形扩环氮杂环卡宾钯化合物具有很好的应用前景。

Claims (1)

1.结构式如下的含吡啶甲基的扩环氮杂环卡宾钯化合物在催化C-N偶联反应中的应用，其特征在于，通过如下步骤实现：
，
将含吡啶甲基的扩环氮杂环卡宾钯化合物催化剂、碱、卤代芳烃、胺加入到溶剂中，在微波辐射下于50~100℃反应10~40分钟后，降至室温，减压除去溶剂，柱色谱分离得到芳胺。
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