CN107964028B - 一种钴络合物及其制备方法与在选择性催化氰基的转移氢化反应中的应用 - Google Patents

一种钴络合物及其制备方法与在选择性催化氰基的转移氢化反应中的应用 Download PDF

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CN107964028B
CN107964028B CN201610911991.8A CN201610911991A CN107964028B CN 107964028 B CN107964028 B CN 107964028B CN 201610911991 A CN201610911991 A CN 201610911991A CN 107964028 B CN107964028 B CN 107964028B
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刘强
付绍敏
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Abstract

本发明公开了一种钴络合物及其制备方法与在选择性催化氰基的转移氢化反应中的应用。所述钴络合物的结构式如式Ⅰ所示。所述钴络合物可通过如下方法制备：在惰性气氛的保护下，钴盐与NNP配体或PNP配体进行反应即得；所述钴盐的化学式为CoX1 2，其中，X1表示卤素、硫酸根、高氯酸根、六氟磷酸根、六氟锑酸根、四氟硼酸根、三氟甲基磺酸根或四(五氟苯基)硼酸根。本发明提供的钴络合物能够用于选择性催化氰基的转移氢化反应，获得一级胺化合物、二级胺化合物和三级胺化合物，它们均为后续一系列的功能化反应中都是重要的中间体，表现出了很高的催化活性，具有很高的研究价值和应用前景。

Description

一种钴络合物及其制备方法与在选择性催化氰基的转移氢化 反应中的应用
技术领域
本发明涉及一种钴络合物及其制备方法与在选择性催化氰基的转移氢化反应中的应用，属于金属络合物技术领域。
背景技术
催化不饱和化合物的氢化反应在化学工业中是一类非常重要的反应。目前，这类氢化反应通常使用的是贵金属催化剂，例如，铱、钌、铑、钯和铂。然而，这些贵金属不仅价格昂贵，而且毒性较高，这无疑会限制上述反应的广泛应用。因此，发展廉价低毒的过渡金属催化剂将具有重要意义。
钴作为地球富含的元素，廉价易得，并且它是维生素B12的重要组成元素，在生命体内广泛存在，生物毒性很小。在之前的研究表明，钴催化剂已经可以很好的实现C＝C双键、C＝O双键、C＝N双键以及氰基的催化氢化反应。其中，对于氰基的还原通常会面临化学选择性还原的问题，例如，如何化学选择性还原得到一级胺、二级胺化合物，将是一个很大的挑战。
发明内容
本发明的目的是提供一种新型的钴-NNP和钴-PNP络合物，本发明络合物能通过不同的配体结构，在不同溶剂和温度下，化学选择性合成各级胺化合物，表现了出很高的催化活性，具有很好研究价值和应用前景。
本发明所提供的钴络合物的结构式如式Ⅰ所示：
式Ⅰ中，表示NNP配体或PNP配体；
X1表示卤素、硫酸根、高氯酸根、六氟磷酸根、六氟锑酸根、四氟硼酸根、三氟甲基磺酸根或四(五氟苯基)硼酸根。
所述NNP配体的结构式如式Ⅱ或式Ⅲ所示：
式Ⅱ和式Ⅲ中，Y表示-CH2-、-NH-或-O-；A表示C或N；
式Ⅱ中，a为0～4之间的整数；n为2～4之间的自然数；
R1表示C1～C6烷基；
R2、R3、R4和R5均独立地表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基或噻吩基；
式Ⅲ中，R6表示C1～C6烷基；
R7、R8、R9、R10、R11和R12分均独立地表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基或噻吩基。
所述PNP配体的结构式如式Ⅳ所示：
式Ⅳ中，R13表示C1～C6烷基。
其中，C1～C6烷基具体指的是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、环戊基、正己基、异己基、新己基、仲己基、叔己基或环己基。
C1～C6烷氧基为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、环戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基或环己氧基。
本发明所述钴络合物具体如式1-式8所示：
各式中，tBu表示叔丁基，Ph表示苯基，Cy表示环己基，iPr表示异丙基。
本发明进一步提供了所述钴络合物的制备方法，包括如下步骤：
在惰性气氛的保护下，钴盐与所述NNP配体或所述PNP配体进行反应，即得所述钴络合物；
所述钴盐的化学式为CoX1 2，其中，X1表示卤素、硫酸根、高氯酸根、六氟磷酸根、六氟锑酸根、四氟硼酸根、三氟甲基磺酸根或四(五氟苯基)硼酸根。
上述的制备方法中，所述钴盐与所述NNP配体或所述PNP配体的摩尔比可为1：1.05～1.1，如1：1.1；
所述反应的温度可为0～40℃，时间可为6～10小时，如在25℃下反应8～12小时、8小时、10小时或12小时。
上述的制备方法中，所述反应在溶剂中进行，所述溶剂可为二氯甲烷、甲醇、乙醇、异丙醇、正丁醇、叔丁醇、甲苯、苯、正己烷、乙酸乙酯、丙酮、三氯甲烷、1,2-二氯甲烷、乙醚、四氢呋喃、水、N,N-二甲基甲酰胺和二甲基亚砜中至少一种。
本发明提供的钴络合物能够用于选择性催化氰基的转移氢化反应，获得一级胺化合物、二级胺化合物和三级胺化合物，它们均为后续一系列的功能化反应中都是重要的中间体。
所述氰基的转移氢化反应的反应方程式具体如式(1)、式(2)或式(3)所示：
式(1)、式(2)和式(3)所示反应方程式中，[Co]表示所述钴络合物；
R14和R15独立地表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基、噻吩基、4-吡啶基、乙酯基或苄氧亚甲基；
R16和R17独立地表示H、C1～C6烷基或苯基。
所述氰基的转移氢化反应在惰性气氛的保护下进行，如在氩气气氛中进行；
所述氰基的转移氢化反应在如下溶剂中进行：甲醇、乙醇、异丙醇、正丁醇、叔丁醇、甲苯、苯、正己烷、乙酸乙酯、丙酮、三氯甲烷、1,2-二氯甲烷、乙醚、四氢呋喃、水和六氟异丙醇中至少一种。
所述氰基的转移氢化反应中，氨基硼烷的摩尔用量可为氰基化合物或二级胺化合物的0.5～3倍；
所述钴络合物的摩尔用量可为氰基化合物或二级胺化合物的0.25％～3％；
所述氰基的转移氢化反应的体系中氰基化合物或二级胺化合物的浓度可为0.1～0.5M；
所述氰基的转移氢化反应的温度可为0～80℃，时间可为0.5～48小时；
所述氨基硼烷的分子式为R15NH2-BH3；
所述氰基化合物的分子式为
所述二级胺化合物的分子式为
各分子式中，R14和R15均表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基、噻吩基、4-吡啶基、乙酯基或苄氧；
R16表示H、C1～C6烷基和苯基。
本发明取得了如下技术效果：
1、本发明提供的新型的钴-NNP或者PNP络合物，为三齿NNP或PNP配体和钴盐的络合物，该新型钴-NNP或者PNP络合物能够化学选择性的催化氰基的转移氢化反应得到一级胺化合物、二级胺化合物和三级胺化合物，表现出了很高的催化活性，具有很高的研究价值和应用前景。
2、本发明还提供了一种制备钴-NNP或者PNP络合物的方法，通过三齿的NNP或者PNP配体与钴盐在溶剂中搅拌反应，过滤所得沉淀即是新型钴-NNP或者PNP络合物，制备简单，易操作。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
下列实施实例中，Me表示甲基，tBu表示叔丁基，nBu表示正丁基，Ph表示苯基，Bn表示苯甲基，Cy表示环己基，iPr表示异丙基，PE表示石油醚，EA表示乙酸乙酯，TLC表示薄层色谱，NMR表示核磁共振。
下述实施例中的配体双[2-(二叔丁基膦基)乙基]胺(tBuPNP)、双[2-(二环己基膦基)乙基]胺(CyPNP)和双[2-(二异丙基膦基)乙基]胺(iPrPNP)，从Alfa-Aesar试剂公司购买，纯度>95％；其余配体均参考文献合成：(Organometallics2003,22,445.；Organometallics,2009，28,6331.；Organometallics2012,31,5239.；Dalton Trans.,2011,40,10397.)。
CoCl2从Alfa-Aesar试剂公司购买，纯度>97％，直接使用。
所用溶剂均从上海国药试剂公司购买，使用前用标准方法提纯干燥。
一、Py-imine-NNP配体和Py-NNP-配体的制备：
1、合成2-氯代-N,N-二(三甲基硅基)乙基胺
往史莱克瓶中先后加入2-氯代乙胺盐酸盐(4.6g,40mmol),NEt3(18mL,132mmol)和的二氯甲烷50mL。反应在室温搅拌的情况下，往该体系加入三甲基氯硅烷(90mmol,9.8g，11.4mL)的二氯甲烷溶液(20mL)。反应室温搅拌过夜，反应结束后，减压除去过量的三乙胺，三甲基氯硅烷和二氯甲烷，往所得的剩余物中加入60mL的正己烷，反应室温搅拌30分钟，过滤除去NEt3·HCl。滤液浓缩后，经过减压蒸馏得到目标产物(6.0g,68％)。1H NMR(400MHz,CDCl3)δ3.37–3.21(m,2H),3.18–2.99(m,2H),0.14(s,18H).13C NMR(101MHz,CDCl3)δ47.38,44.83,1.89.
2、合成2-叔丁基膦乙胺
在氩气条件下，往100mL的史莱克瓶中，加入二叔丁基膦(2.92g,20mmoL)和正己烷(20ml)，将上述混合液冷却到-78度，往该体系中逐滴加入正丁基锂(2.5M,8.8mL,22mmoL)。加完后，反应升至室温，继续搅拌1h后，得到LiPtBu2白色悬浊物。
在氩气保护下，将2-氯代-N,N-二(三甲基硅基)乙基胺(4.46g,20mmoL)和20mL正己烷，加入到史莱克瓶中，在搅拌情况下，往该混合物加入上述LiPtBu2的悬浊液。反应室温搅拌30min后，加热回流8h。反应结束后，往反应中加入10mL脱气水和2M 10mL的H2SO4溶液，反应室温搅拌一小时，之后往该反应中加入11mL 4M NaOH溶液，反应继续搅拌一小时。分离有机相，水相用正己烷萃取(2×15mL)，合并有机相，无水硫酸钠干燥，过滤，抽干后得粗品2-叔丁基膦乙胺，后经减压蒸馏，得到纯品(2.3g,61％)。1H NMR(400MHz,CDCl3)δ2.82(dd,J＝15.4and 7.9Hz,2H),1.53-1.48(m,2H),1.41(br,2H),1.12(d,J＝11.1Hz,18H).13C NMR(101MHz,CDCl3)δ43.85(d,JC-P＝30.3Hz),31.04(d,JC-P＝19.2Hz),29.59(d,JC-P＝13.1Hz),26.18(d,JC-P＝20.2Hz).31P NMR(162MHz,CDCl3)δ20.45(s).
3-1、合成Py-imine-NNP配体
在氩气条件下，往史莱克瓶中，加入2-吡啶甲醛(0.139g,1.3mmoL)和5mL脱气THF，往该溶液中加入2-叔丁基膦乙胺的(0.246g,1.3mmoL)的THF(5mL)溶液。反应搅拌0.5h，将THF溶剂抽干，得吡啶-imine-NNP配体(0.35g,98％)。1H NMR(400MHz,CDCl3)δ8.66(d,J＝4.7Hz,1H),8.42(s,1H),7.98(d,J＝7.9Hz,1H),7.75(t,J＝7.7Hz,1H),7.34–7.30(m,1H),3.87-3.82(m,2H),1.84-1.78(m,2H),1.17(d,J＝11.2Hz,18H).13C NMR(101MHz,CDCl3)δ161.62,154.52,149.49,136.51,124.64,121.37,62.54(d,JC-P＝34.3Hz),31.31(d,JC-P＝20.2Hz),29.58(d,JC-P＝14.1Hz),23.08(d,JC-P＝20.2Hz).31P NMR(162MHz,CDCl3)δ24.45.
3-2、合成Py-NNP-配体
在氩气条件下，往史莱克瓶中，加入2-吡啶甲醛(0.139g,1.3mmoL)和5ml THF，在搅拌的情况下，往该溶液中加入2-叔丁基膦乙胺的(0.246g,1.3mmol)的THF(5mL)溶液。反应搅拌半小时后，将溶剂抽干。所得的反应剩余物重新溶解于10mL甲苯，往该溶液中缓慢滴加1.2M的DIBAL的甲苯溶液(1.3mL,1.56mmoL)。反应室温搅拌0.5小时后，加入3mL水淬灭，甲苯萃取两次(2×5mL)，合并有机相。硫酸钠干燥，过滤，将溶剂抽干后得吡啶NNP配体(0.320g,89％)。1H NMR(400MHz,CDCl3)δ8.48(d,J＝4.2Hz,1H),7.56(t,J＝8.0Hz,1H),7.21(d,J＝11.3Hz,1H),7.08(t,J＝6.2Hz,1H),3.87(s,2H),2.74(dd,J＝16.3and 7.2Hz,2H),1.98(s,1H),1.59(td,J＝8.2and4.4Hz,2H),1.06(d,J＝11.1Hz,18H).13C NMR(101MHz,CDCl3)δ159.74,149.30,136.40,122.24,121.88,55.14,50.54(d,JC-P＝32.4Hz),31.13(d,JC-P＝19.3Hz),29.58(d,JC-P＝13.3Hz,),22.18(d,JC-P＝19.7Hz).31P NMR(162MHz,CDCl3)δ22.70(s).
二、N-Me-Py-NNP配体的制备
1、合成二叔丁基膦硼烷络合物
在氩气保护条件下，往溶解有二叔丁基膦(2.92g,20.0mmol)的脱气THF溶液中，加入BH3·THF溶液(24mL of 1M solution in THF,24mmol)。反应室温搅拌4h后，抽干溶剂，得白色固体(2.74g,90％).1H NMR(400MHz,CDCl3)δ3.84(1JH-P＝345Hz,3JH-H＝6.5Hz,1H),1.25(d,J＝13.6Hz,18H),0.57(m brw,3H).13C NMR(101MHz,CDCl3)δ30.5(d,JC-P＝27.5Hz),28.9.31P NMR(162MHz,CDCl3)δ48.00(q).
2、合成2-二叔丁基膦乙胺硼烷络合物
在氩气条件下，往100mL的史莱克瓶中，加入二叔丁基膦硼烷络合物(1.52g,10mmol)和正己烷(20ml)，将上述混合液冷却到-78度，往该体系中逐滴加入正丁基锂(2.5M,8.8mL,22mmoL)。加完后，反应升至室温，继续搅拌1h后，得到tBu2PLi·BH3白色悬浊物。
在氩气保护下，将2-氯代-N,N-二(三甲基硅基)乙基胺(2.23g,10mmoL)和20mL正己烷，加入到史莱克瓶中，在搅拌情况下，往该混合物加入上述tBu2PLi·BH3白色悬浊物。反应室温搅拌30min后，加热回流24h。反应结束后，将反应降至0度，往反应中加入5mL脱气水和2M 6mL的H2SO4溶液，反应搅拌一小时，之后往该反应中加入7mL 4M NaOH溶液，反应继续搅拌一小时。分离有机相，水相用正己烷萃取(2×15mL)，合并有机相，无水硫酸钠干燥，过滤，旋干后，剩余物经柱色谱层析(CH2Cl2/CH3OH＝50:1 to 16:1)得目标产物(1.15g,57％).1H NMR(400MHz,CDCl3)δ3.04(dd,J＝15.4,7.6Hz,2H),1.90(s,2H),1.83–1.72(m,2H),1.25(d,J＝12.5Hz,18H),0.54(m brw,3H).13C NMR(101MHz,CDCl3)δ38.6,32.0(d,JC-P＝27.3Hz),27.7,22.1(d,JC-P＝26.8Hz).31P NMR(162MHz,CDCl3)δ40.87(q).HR-MS(ESI)calcd.for C10H28BNP[M+H]+:204.2047；found:204.20381.
3、合成Py-NNP-硼烷络合物
在氩气条件下，往史莱克瓶中，加入2-吡啶甲醛(0.268g,2.5mmoL)和8ml THF，在搅拌的情况下，往该溶液中加入2-叔丁基膦乙胺的硼烷络合物(0.507g,2.5mmol)的THF(8mL)溶液。反应搅拌半小时后，将溶剂抽干。所得的反应剩余物重新溶解于15mL甲苯，往该溶液中缓慢滴加1.2M的DIBAL的甲苯溶液(1.2M,2.3mL,2.75mmol).。反应室温搅拌0.5小时后，加入3mL水淬灭，乙醚萃取两次(2×5mL)，合并有机相。硫酸钠干燥，过滤，将溶剂抽干后，所得剩余物经柱层析过柱(CH2Cl2/CH3OH＝50:1 to 16:1)得目标产物(0.53g,73％)。1HNMR(400MHz,CDCl3)δ8.48(d,J＝4.7Hz,1H,Py-H),7.57(td,J＝7.7,1.7Hz,1H,Py-H),7.29–7.18(m,1H,Py-H),7.09(dd,J＝6.9,5.3Hz,1H,Py-H),3.86(s,2H,Py-CH2),3.06–2.85(m,2H,N-CH2),2.08(s,1H,NH),1.91–1.72(m,2H,P-CH2),1.18(d,J＝12.5Hz,18H,2×tBu),0.44(m brw,3H,BH3).13C NMR(101MHz,CDCl3)δ159.3(Py-H),149.3(Py-H),136.5(Py-H),122.3(Py-H),122.0(Py-H),54.9(Py-CH2),45.7(NH-CH2),32.1(d,JC-P＝27.3Hz,P-CH2),27.7(CMe3),18.8(d,J＝27.9Hz,CMe3).31P NMR(162MHz,CDCl3)δ41.54(q).HR-MS(ESI)calcd.for C16H33BN2P[M+H]+:295.24689；found:295.24588.
4、合成N-Me-Py-NNP-硼烷络合物
将37％含量的甲醛溶液(0.16g,2.0mmol)加入到含有Py-NNP-硼烷络合物(0.294g,1.0mmol)的1,2-二氯乙烷溶液(10ml).反应搅拌15分钟后，往该反应溶液中，分批加入NaBH(OAc)3(0.424g,2.0mmol)，加完后，反应室温搅拌过夜。反应结束后，用2M氢氧化钠(10mL)淬灭。分离出有机相，水相用二氯甲烷萃取三次(3×10mL)，合并有机相，硫酸镁干燥，过滤，滤液旋干，所得剩余物经柱层析色谱分离(石油醚/乙酸乙酯/甲醇＝3:1:0.2)得目标产物(0.20g,67％)。
1H NMR(400MHz,CDCl3)δ8.55(d,J＝4.7Hz,1H,Py-H),7.65(td,J＝7.7,1.6Hz,1H,Py-H),7.38(d,J＝7.8Hz,1H,Py-H),7.16(dd,J＝6.8,5.5Hz,1H,Py-H),3.71(s,2H,Py-CH2),2.91–2.63(m,2H,N-CH2),2.32(s,3H,N-Me),1.96–1.75(m,2H,P-CH2),1.23(d,J＝12.5Hz,18H,2×tBu),0.48(m brw,3H).13C NMR(101MHz,CDCl3)δ158.9(Py-C),149.2(Py-C),136.3(Py-C),123.2(Py-C),121.9(Py-C),63.2(Py-CH2),53.2(N-CH2),42.2(N-Me),32.1(d,JC-P＝27.1Hz,P-CH2),27.7(CMe3),15.6(d,JC-P＝27.1Hz,CMe3).31P NMR(162MHz,CDCl3)δ42.22(q).HR-MS(ESI)calcd.for C17H35BN2P[M+H]+:309.26254；found:309.26190.
5、合成N-Me-Py-NNP配体
在氩气氛围下，往含有N-Me-Py-NNP-硼烷络合物的25ml史莱克瓶中，加入12ml二乙胺，反应90度进行18h。之后，抽干溶剂，剩余物转移至手套箱，经柱层析分离(CH2Cl2/CH3OH＝40:1 to 30:1)得目标产物(0.12g,68％).。
1H NMR(400MHz,CDCl3)δ8.54(d,J＝4.6Hz,1H,Py-H),7.64(td,J＝7.7,1.7Hz,1H,Py-H),7.42(d,J＝7.8Hz,1H,Py-H),7.15(dd,J＝7.0,5.3Hz,1H,Py-H),3.71(s,2H,Py-CH2),2.73–2.54(m,2H,N-CH2),2.32(s,3H,N-Me),1.68–1.56(m,2H,P-CH2),1.11(d,J＝11.1Hz,18H,2×tBu).13C NMR(101MHz,CDCl3)δ149.2(Py-C),136.3(Py-C),123.2(Py-C),121.9(Py-C),63.4(Py-CH2),58.9(d,JC-P＝37.1Hz,N-CH2),42.2(N-Me),31.2(d,JC-P＝19.8Hz,N-CH2),29.6(d,JC-P＝13.5Hz,CMe3),18.9(d,JC-P＝20.0Hz,CMe3).31P NMR(162MHz,CDCl3)δ25.18.HR-MS(ESI)calcd.for C17H32N2P[M+H]+:295.22976；found:295.22855.
实施例1、合成吡啶NNP-CoCl2络合物(式2所示)
反应方程式如下所示：
将溶解了吡啶NNP配体(0.28g，1.0mmol)的脱气THF(5ml)溶液加入二氯化钴(0.115g，0.90mmol)的THF(5ml)中，配体加完后，反应悬浊液颜色由蓝色变为粉色，反应室温(25℃)搅拌12h，之后将溶液浓缩至2ml，加入15ml脱气正己烷，搅拌1小时后，氩气过滤，所得滤饼干燥后，得粉色固体(0.339g，83％)。
元素分析：理论值(％)：C,46.84；H,7.13；N,6.83；实测:C,46.82；H,7.34；N,6.62.
核磁1H NMR(400MHz,CD2Cl2)δ＝50.72(br),44.82(br),41.24(br),34.48(br),3.27(br),2.57(br),2.32(br),1.37(br),-2.88(br).
磁距:4.3μB.
红外(KBr):3430,2951,1607,1475,1431,1360,1295,1193,1099,1019,905,889,814,776cm-1.
由上述分析结果可知所制备的目标化合物结构正确。
实施例2、合成Py-imine-NNP-CoCl2络合物(式3所示)
反应方程式如下所示：
将溶解了Py-imine-NNP配体(0.278g，1.0mmol)的脱气THF(5mL)溶液加入二氯化钴(0.115g，0.90mmoL)的THF(5mL)中，配体加完后，反应室温(25℃)搅拌8h，之后将溶液浓缩至2mL，加入15ml脱气正己烷，搅拌1小时后，氩气过滤，所得滤饼干燥后，得褐色固体(0.330g，91％)。
元素分析：理论值(％)：C,47.08；H,6.67；N,6.86；实测:C,46.60；H,6.37；N,7.12.
核磁：1H NMR(400MHz,CD2Cl2)δ＝60.94(br),51.19(br),48.81(br),3.48(br),1.94(br),0.90(br),-0.59(br).
磁距:4.2μB.
红外：(KBr):3433,3060,2944,2867,1653,1600,1567,1470,1445,1394,1372,1299,1180,1152,1104,1015,942,869,819,776,689,638,514cm-1.
由上述分析结果可知所制备的目标化合物结构正确。
实施例3、合成tBuPNP-CoCl2络合物(式8所示)
反应方程式如下所示：
将溶解了tBuPNP配体(0.361g，1.0mmol)的THF(5ml)溶液加入二氯化钴(0.115g,0.90mmol)的THF(5ml)中，配体加完后，反应室温(25℃)搅拌10h，之后将溶液浓缩至2ml，加入15ml脱气正己烷，搅拌1小时后，氩气过滤，所得滤饼干燥后，得蓝色固体(0.387g，88％)。
元素分析：理论值(％)：C,48.89；H,9.23；N,2.85；found:C,48.42；H,9.06；N,3.02.
核磁：1H NMR(400MHz,CD2Cl2)δ＝7.24(br),3.34(br),1.42(br),1.18(br),1.15(br),1.05(br),0.80(br),-1.96(br),-4.56(br).
磁距:4.5μB.
红外(KBr):3214,2939,2865,1468,1390,1371,1177,1130,1080,1022,934,814,772,692,602,579 466cm-1.
由上述分析结果可知所制备的目标化合物结构正确。
按照与实施例1-3相同的方法制备得到了式1、式4、式5、式6和式7所示钴络合物：
实施例4、不同钴络合物催化氰基转移氢化反应效果比较
表1不同钴络合物催化氰基转移氢化反应效果比较
[a]反应条件:0.5mmol苯甲腈,0.8mmol氨硼烷,2mL MeOH,0.5mol％催化剂,25℃,13h.[b]产率以联苯作为内标GC定量.[c]不加催化剂.
(1)钴催化氰基转移氢化合成一级胺的合成步骤
在氩气的保护下，将催化剂式1所示络合物(2.1mg,0.005mmol,1mol％),氨硼烷(24.9mg,0.8mmol,1.6equiv)，苯甲腈(0.5mmol)和甲醇(1mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应50℃反应16小时。反应结束后，用5mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
(2)钴催化氰基转移氢化合成对称二级胺化合物的合成步骤：
在氩气的保护下，将催化剂式2所示络合物(1.1mg,0.0025mmol,0.5mol％),氨硼烷(24.9mg,0.8mmol,1.6equiv)，苯甲腈(0.5mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25℃反应13小时。反应结束后，减压除去溶剂，剩余物经柱层析硅胶(PE/EA＝10:1)分离，得二级胺化合物。
(3)钴催化氰基转移氢化合成不对称二级胺化合物的合成步骤
在氩气的保护下，将催化剂式2所示络合物(1.1mg,0.0025mmol,0.5mol％),氨硼烷(24.9mg,0.8mmol,1.6equiv)，苯甲腈(0.6mmol)，胺类化合物(0.5mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25℃反应13小时。反应结束后，减压除去溶剂，剩余物经柱层析硅胶分离，得不对称二级胺化合物。
由表1中的数据可以看出，钴催化剂在甲醇作为溶剂条件下主要生成二级胺，且不加配体或者不加催化剂情况下，反应不能催化氰基的转移氢化反应。
实施例5、不同溶剂对于钴催化剂(式1所示络合物)催化氰基转移氢化反应的影响
在氩气的保护下，将催化剂式1所示络合物(2.1mg,0.005mmol,1mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.5mmol)和溶剂(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，50℃下反应16小时。反应结束后，用5mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
表2溶剂效应对于钴催化氰基转移氢化反应的影响
[a]反应条件:0.5mmol苯甲腈,0.8mmol氨硼烷,2mL n-hexane,1mol％催化剂,50℃,16h.[b]产率以联苯作为内标用GC进行定量.
由表2中的数据可以看出，反应溶剂效应对产物的选择性影响很明显，非质子性溶剂的化学选择性要明显好于质子性溶剂，溶剂优化表明，以正己烷作为溶剂，络合物1作为催化剂，可以高选择性的得到一级胺化合物。
实施例6、钴催化剂(式1所示络合物)催化氰基转移氢化反应的条件优化
在氩气的保护下，将催化剂式1所示络合物(0.5-1mol％)、氨硼烷(0.6-1.5equiv)、苯甲腈(0.5mmol)和正己烷(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，25～50℃下反应16小时。反应结束后，用5mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
由表3中的数据可以看出，提高或者降低催化剂的用量都会降低一级胺化合物的产率，此外，降低温度也会降低该反应产率。将氨硼烷的用量从1.5当量降低到催化计量0.8当量时，反应产率能继续提高至91％。
表3催化剂和氨硼烷当量以及温度对钴催化氰基转移氢化反应的影响a
[a]反应条件:0.5mmol苯甲腈和0.5mmol氨硼烷,2mL正己烷和在给定的催化剂I和温度下反应16小时[b]产率以联苯作为内标用GC进行定量.
[c]1ml正己烷.[d]0.5ml正己烷.
实施例7、不同溶剂对于钴催化剂(式2所示络合物)催化氰基转移氢化反应的影响
氩气的保护下，将催化剂(式2所示络合物)(1.1mg,0.0025mmol,0.5mol％),氨硼烷(24.9mg,0.8mmol,1.6equiv)，苯甲腈(0.5mmol)和溶剂(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25度反应13小时。反应结束后，用5mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
表4不同溶剂对于钴(式2所示络合物)催化氰基转移氢化反应的影响
[a]反应条件:0.5mmol苯甲腈,0.8mmol氨硼烷，2ml溶剂和0.5mol％催化剂II,25℃,13h.[b]产率以联苯作为内标用GC进行定量.
由表4中的数据可以看出，以式2所示络合物作为催化剂，在极性溶剂条件下，反应主要生成二级胺化合物，其中以六氟异丙醇(HFIP)作为溶剂时，反应能以88％产率得到目标化合物。
实施例8、钴催化剂(式1所示络合物)催化氰基的转移氢化合成一级胺的底物拓展
在氩气的保护下，将催化剂式1所示络合物(2.1mg,0.005mmol,1mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.5mmol)和正己烷(1mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，50℃反应16小时。反应结束后，用5mL甲醇稀释反应混合物，反应产物以联苯作为内标进行GC定量。
表5钴(式1所示络合物)催化氰基的转移氢化合成一级胺化合物
反应条件：催化剂1(0.5mmol),氨硼烷(0.8mmol)和1mL正己烷,GC产率以联苯作为内标用GC进行定量.[a]反应在100℃进行.[b]反应在120℃进行。
由表5中的数据可以看出，催化反应条件温和，底物兼容性很好，芳环上无论是给电子基(甲基、甲氧基)或者是吸电子基(酯基、三氟甲基)都能很好的兼容，此外，卤素取代基(氟，氯，溴和碘)都能以高产率得到相应的一级胺化合物。杂环以及烷基腈都能以中等到优良的收率得到相应的产率。1,6-己二胺作为重要的化工原料也可以在该催化条件下，催化还原1,4-己二腈的还原反应得到。
实施例9、钴催化剂(式2所示络合物)催化氰基的转移氢化反应合成对称二级胺的底物拓展
氩气的保护下，将催化剂式2所示络合物(1.1mg,0.0025mmol,0.5mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.5mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，25℃反应13小时。反应结束后，用5mL甲醇稀释反应混合物。减压除去溶剂，剩余物经柱层析硅胶分离，得反式烯烃产物。
表6钴催化(式2所示络合物)氰基的转移氢化合成对称二级胺化合物
反应条件:0.5mmol腈化合物,0.8mmol氨硼烷，2mL六氟异丙醇,分离产率(％)[a]反应在50℃进行.HFIP＝Hexafluoroisopropanol.
由表6中的数据可以看出，钴催化剂催化反应条件温和，底物兼容性很好，芳环上无论是给电子基(甲基、甲氧基)或者是吸电子基(酯基、三氟甲基)都能很好的兼容，此外，卤素取代基(氟、氯、溴和碘都)能以高产率得到相应的对称的二级胺化合物，而氰基乙酸乙酯同样可以中等偏低的产率得到对称的二级胺化合物。
实施例10、钴催化剂(式2所示钴络合物)催化氰基的转移氢化反应合成不对称二级胺的底物拓展
氩气的保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.5mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.5mmol)，胺类化合物和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，25℃反应13小时。反应结束后，用5mL甲醇稀释反应混合物。减压除去溶剂，剩余物经柱层析硅胶分离，得不对称的二级胺化合物。
表7钴(式2所示钴络合物)催化氰基的转移氢化合成不对称二级胺
反应条件:0.6mmol腈化合物,0.5mmol胺化合物,0.8mmol氨硼烷和2mL六氟异丙醇,分离产率(％).[a]0.5mmol腈化合物,0.6mmol胺化合物.[b]0.6mmol腈化合物,2mmol胺化合物.[c]0.5mmol腈化合物,1mmol胺化合物.[d]反应在2ml正己烷100℃下进行.
由表7中的数据可以看出，该反应同样可以催化各种芳基以及烷基胺与腈类化合物以中等到优良的收率得到不对称的二级胺化合物，该反应还可以选择性的N-烷基化手性的氨基醇化合物。此外，三级胺化合物也可以在该催化条件下利用二级胺与腈类化合物反应得到。
实施例11、钴催化氰基化合物和胺类药物的苄基化反应
氩气的保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.5mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.5mmol)、胺类药物(0.5mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25度反应13小时。反应结束后，用5mL甲醇稀释反应混合物。减压除去溶剂，剩余物经柱层析硅胶分离，得不对称的二级胺化合物。
表8钴催化氰基化合物和胺类药物的苄基化反应
由表8中的数据可以看出，该钴催化反应对于含一级胺或者二级胺药物的后期苄基化反应都能很好的适用，以良好到优秀的产率得到苄基化产物。
实施例12、钴催化三种不同的氰基化合物合成不对称三级胺化合物
在氩气的保护下，将催化剂式1所示钴络合物(2.1mg,0.005mmol,1mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、对甲氧基苯甲腈(0.5mmol)和正己烷(1mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应50度反应16小时。反应结束后，用5mL甲醇稀释反应混合物，反应产物以联苯作为内标进行GC定量。
氩气的保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.5mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、苯甲腈(0.6mmol)，对甲氧基苄胺(0.5mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25度反应12小时。反应结束后，用5mL甲醇稀释反应混合物。减压除去溶剂，剩余物经柱层析硅胶分离，得不对称的二级胺化合物。
氩气的保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.5mol％)、氨硼烷(24.9mg,0.8mmol,1.6equiv)、不对称二级胺化合物(0.6mmol)，对氯苯甲腈(0.6mmol)和六氟异丙醇(2mL)先后加入到含磁力搅拌子的25mL史莱克瓶中，反应25度反应12小时。反应结束后，用5mL甲醇稀释反应混合物。减压除去溶剂，剩余物经柱层析硅胶分离，得不对称的三级胺化合物。
由该实施例可以看出，可以利用不同的钴催化剂在不同的溶剂和温度下，从苯甲腈出发，通过三步合成不对称的三级胺化合物，每步反应催化剂用量低且产率高，具有很大的应用前景。
实施例13、考察钴催化剂(式2所示钴络合物)催化氰基化合物合成不对称二级胺化合物的TON实验
氩气保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.025mol％)、氨硼烷(498mg,16mmol,1.6equiv)、苯甲腈(1.02mL,10mmol)和六氟异丙醇(15mL)先后加入到含磁力搅拌子的50mL耐压瓶中，75℃反应20小时。反应结束后，用15mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
氩气保护下，将催化剂式2所示钴络合物(1.1mg,0.0025mmol,0.025mol％)、氨硼烷(996mg,32mmol,1.6equiv)，苯甲腈(1.02mL,10mmol)，苯胺(1.82mL,20mmol)和六氟异丙醇(25mL)先后加入到含磁力搅拌子的50mL耐压瓶中，反应25度反应13小时。反应结束后，用15mL甲醇稀释反应混合物。反应产物以联苯作为内标进行GC定量。
由该实施例可以看出，上述钴催化剂催化氰基的转移氢化反应，TON(转化数)超过2000，显示出了很高的催化活性和稳定性。
由上述实施例可以看出，本发明提供了一类新型的钴-NNP或者钴-PNP络合物，该络合物是三齿NNP或者PNP配体和钴盐的络合物，该新型钴络合物能够催化氰基化合物的转移氢化反应，化学选择性的合成一级、二级和三级胺化合物，表现出了很高的催化活性，具有很高的研究价值和应用前景。
在此说明书中，本发明已经参照特定的实施实例做了描述。但是，很显然仍可以作出各种修改和变换而不背离本发明的精神和范围。

Claims (8)

1.一种钴络合物，其结构式如式Ⅰ所示：
式Ⅰ中，表示NNP配体；
X1表示卤素、硫酸根、高氯酸根、六氟磷酸根、六氟锑酸根、四氟硼酸根、三氟甲基磺酸根或四(五氟苯基)硼酸根；
所述NNP配体的结构式如式Ⅱ或式Ⅲ所示：
式Ⅱ和式Ⅲ中，Y表示-CH2-；A表示C或N；
式Ⅱ中，a为0～4之间的整数；n为2；
R1表示C1～C6烷基；
R2、R3、R4和R5均独立地表示H；
式Ⅲ中，R6表示C1～C6烷基；
R7表示甲基；R8、R9、R10、R11和R12均独立地表示H。
2.权利要求1所述钴络合物的制备方法，包括如下步骤：
在惰性气氛的保护下，钴盐与所述NNP配体进行反应，即得所述钴络合物；
所述钴盐的化学式为CoX1 2，其中，X1表示卤素、硫酸根、高氯酸根、六氟磷酸根、六氟锑酸根、四氟硼酸根、三氟甲基磺酸根或四(五氟苯基)硼酸根。
3.根据权利要求2所述的制备方法，其特征在于：所述钴盐与所述NNP配体的摩尔比为1：1.05～1.1；
所述反应的温度为0～40℃，时间为6～10小时。
4.根据权利要求2或3所述的制备方法，其特征在于：所述反应在溶剂中进行，所述溶剂为二氯甲烷、甲醇、乙醇、异丙醇、正丁醇、叔丁醇、甲苯、苯、正己烷、乙酸乙酯、丙酮、三氯甲烷、1,2-二氯甲烷、乙醚、四氢呋喃、水、N,N-二甲基甲酰胺和二甲基亚砜中至少一种。
5.权利要求1所述钴络合物在选择性催化氰基的转移氢化反应中的应用。
6.根据权利要求5所述的应用，其特征在于：所述氰基的转移氢化反应的反应方程式如式(1)、式(2)或式(3)所示：
式(1)、式(2)和式(3)所示反应方程式中，[Co]表示权利要求1所述钴络合物；
R14和R15独立地表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基、噻吩基、4-吡啶基、乙酯基或苄氧亚甲基；
R16和R17独立地表示H、C1～C6烷基或苯基。
7.根据权利要求5或6所述的应用，其特征在于：所述氰基的转移氢化反应在惰性气氛的保护下进行；
所述氰基的转移氢化反应在如下溶剂中进行：甲醇、乙醇、异丙醇、正丁醇、叔丁醇、甲苯、苯、正己烷、乙酸乙酯、丙酮、三氯甲烷、1,2-二氯甲烷、乙醚、四氢呋喃、水和六氟异丙醇中至少一种。
8.根据权利要求6所述的应用，其特征在于：所述氰基的转移氢化反应中，氨基硼烷的摩尔用量为氰基化合物或二级胺化合物的0.5～3倍；
权利要求1所述钴络合物的摩尔用量为氰基化合物或二级胺化合物的0.25％～3％；
所述氰基的转移氢化反应的体系中氰基化合物或二级胺化合物的浓度为0.1～0.5M；
所述氰基的转移氢化反应的温度为0～80℃，时间为0.5～48小时；
所述氨基硼烷的分子式为R15NH2-BH3；
所述氰基化合物的分子式为
所述二级胺化合物的分子式为
各分子式中，R14和R15均表示H、C1～C6烷基、C1～C6烷氧基、苯基、C1～C6烷基取代苯基、卤素、苄基、羟基、萘基、呋喃基、噻吩基、4-吡啶基、乙酯基或苄氧亚甲基；
R16表示H、C1～C6烷基和苯基。
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