含有二萘基1,2-b;5,6-b’环辛四烯和手性膦氮骨架的π-烯丙基铱络合物、合成方法以及应用

摘要

本发明提供了一种光学纯的具有二萘基[1,2-b;5,6-b’]环辛四烯和手性亚膦酰胺骨架的π-烯丙基铱络合物、其合成方法和这种络合物在金属铱催化的不对称烯丙基取代反应中的应用。该络合物是以[Ir(dncot)Cl]

说明书

技术领域

本发明涉及具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物、合成方法及应用，该方法可以高收率的合成这种络合物，并把该络合物成功的应用于一系列金属铱催化的不对称烯丙基取代反应中。 

背景技术

金属铱催化的不对称烯丙基取代反应可以以高对映选择性、区域选择性的构建碳碳键和碳杂键，在合成中得到了广泛的应用。目前此类反应使用的的催化剂主要是[Ir(cod)Cl]₂和手性膦氮配体。[(a)Miyabe,H.;Takemoto,Y.Synlett2005,1641.(b)Takeuchi,R.;Kezuka,S.Synthesis2006,3349.(c)Helmchen,G.;Dahnz,A.;Dübon,P.;Schelwies,M.;Weihofen,R.Chem.Commun.2007,675.(d)Helmchen,G.;In Iridium Complexes in Organic Synthesis;Oro,L.A.;Claver,C.Eds.;Wiley-VCH:Weinheim,Germany,2009;p211.(e)Hartwig,J.F.;Stanley,L.M.Acc.Chem.Res.2010,43,1461.(f)Hartwig,J.F.;Pouy,M.J.Top.Organomet.Chem.2011,34,169.(g)Liu,W.-B.;Xia,J.-B.;You,S.-L.Top.Organomet.Chem.2012,38,155.(h)Tosatti,P.;Nelson,A.;Marsden,S.P.Org.Biomol.Chem.2012,10,3147.]。然而，这类催化体系空气十分敏感，催化剂的用量也较大，并且对于一些特殊的底物的区域选择性控制不够理想[(a)Streiff,S.;Welter,C.;Schelwies,M.;Lipowsky,G.;Miller,N.;Helmchen,G.Chem.Commun.2005,2957.(b)Welter,C.;Dahnz,A.;Brunner,B.;Streiff,S.;Dübon,P.;Helmchen,G.Org.Lett.2005,7,1239.(c)Gnamm,C.;S.;Miller,N.;K.;Helmchen,G.Synlett2007,790.(d)Gnamm,C.;Franck,G.;Miller,N.;Stork,T.;K.;Helmchen,G.Synthesis2008,3331. 

为了解决这些问题，我们设计合成了一系列具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物，该络合物合成简单，容易通过重结晶提纯，并且在金属铱催化的烯丙基取代反应中具有非常好的效果。尤其是对于一 些特殊的底物，该络合物通常能取得非常好的区域选择性和对映选择性。因此该络合物对于金属铱催化的烯丙基取代反应底物范围的拓展以及反应类型的丰富都具有非常重要的意义。 

发明内容

本发明的目的是提供一种光学纯的具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物、其合成方法和这种络合物在金属铱催化的不对称烯丙基取代反应中的应用。 

本发明的方法是一种有效的用[Ir(dncot)Cl]₂，手性膦氮类化合物、取代烯丙基碳酸酯类化合物、银盐合成具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物。 

本发明所合成的光学纯二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物可以应用在金属铱催化的不对称烯丙基取代反应中，能以高的效率、区域选择性和对映选择性得到产物。 

本发明所述的二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的结构式是： 

或者其(非)对映异构体 

或者其(非)对映异构体 

或者其(非)对映异构体 

或者其(非)对映异构体 

或者其(非)对映异构体 

或者其(非)对映异构体 

的光学纯化合物； 

其中R¹任意选自H、C1-C6的烷基、C1-C6的全氟烷基或芳基及取代的芳基； 

R²,R³,R⁴任意选自H、F、Cl、Br、I、C1-C4的烷基、C1-C4的环烷基、 C1-C4的全氟烷基或芳基及取代的芳基； 

Ar¹、Ar²任意选自芳基及取代的芳基； 

X任意选自CF₃SO₃、ClO₄、SbF₆、BF₄; 

n任意选自1、2或3； 

上述的芳基为苯基、萘基、蒽基、菲基；所述取代芳基上的取代基任意选自H F、Cl、Br、I、C₁～C₁₆的烃氧基、C₁～C₁₆的烷基或C₁～C₁₆的氟代烷基、硝基或氨基。 

本发明所述的具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物是以[Ir(dncot)Cl]₂，手性膦氮类化合物、取代烯丙基碳酸酯类化合物、银盐为原料，在有机溶剂的作用下反应制得，所述的[Ir(dncot)Cl]₂具有如下结构: 

本发明方法，根据具体结构可分别用以下方程式1-24表示： 

方程式1： 

方程式2： 

方程式3： 

方程式4： 

方程式5： 

方程式6： 

方程式7： 

方程式8： 

方程式9： 

方程式10： 

方程式11： 

方程式12： 

方程式13： 

方程式14： 

方程式15： 

方程式16： 

方程式17： 

方程式18： 

方程式19： 

方程式20： 

方程式21： 

方程式22： 

方程式23： 

方程式24： 

以上方程式中，其中R¹任意选自H、C1-C6的烷基、C1-C6的全氟烷基或芳基及取代的芳基； 

R²,R³,R⁴任意选自H、F、Cl、Br、I、C1-C4的烷基、C1-C4的环烷基、C1-C4的全氟烷基或芳基及取代的芳基； 

Ar¹、Ar²任意选自芳基及取代的芳基； 

X任意选自CF₃SO₃、ClO₄、SbF₆、BF₄; 

n任意选自1、2或3； 

上述的芳基为苯基、萘基、蒽基、菲基；所述取代芳基上的取代基任意选自H F、Cl、Br、I、C₁～C₁₆的烃氧基、C₁～C₁₆的烷基或C₁～C₁₆的氟代烷基、硝基或氨基。 

所述反应中的[Ir(dncot)Cl]₂，手性膦氮类化合物、取代烯丙基碳酸酯类化合物、银盐的摩尔比为1-1.5:1-3.5:1-4:2-6；推荐反应的摩尔比为：[Ir(dncot)Cl]₂、 手性膦氮类化合物、取代烯丙基碳酸酯类化合物、银盐的摩尔比为1:2:4:2。反应在温度为25℃至120℃，推荐反应温度为：25℃至80℃。反应时间为24小时－48小时。 

本发明方法中，所述有机溶剂可以是极性或非极性溶剂。如苯、四氯化碳、四氢呋喃、二甲基甲酰胺、乙醚、二氯甲烷、三氯甲烷、甲苯、二甲苯、环己烷、正己烷、正庚烷、二氧六环、乙腈等，推荐溶剂为四氢呋喃。 

采用本发明方法所得的产物具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物可以经过重结晶，薄层层析，柱层析等方法加以分离。如用重结晶的方法，推荐溶剂为极性溶剂与非极性溶剂的混合溶剂。推荐溶剂可为二氯甲烷―正己烷，异丙醇―石油醚，乙酸乙酯―石油醚，乙酸乙酯―正己烷，异丙醇―乙酸乙酯―石油醚等混合溶剂。用薄层层析和柱层析方法，所用的展开剂为极性溶剂与非极性溶剂的混合溶剂。推荐溶剂可为异丙醇―石油醚，异丙醇―二氯甲烷，甲醇-二氯甲烷，乙酸乙酯―石油醚，乙酸乙酯―正己烷，异丙醇―乙酸乙酯―石油醚等混合溶剂，其体积比可以分别是：极性溶剂：非极性溶剂＝1:1－1:500。例如：乙酸乙酯：石油醚＝1:1－1:500，异丙醇：石油醚＝1:1－1:500. 

本发明提供了一种有效的由[Ir(dncot)Cl]₂，手性膦氮类化合物、取代烯丙基碳酸酯类化合物、银盐为原料合成具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的方法。该方法反应条件温和，操作简单原料易得，收率高，提纯方便。 

本发明所提供的具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物，对空气稳定，易于制备和保持。可以应用在金属铱催化的多种不同类型不对称分子间烯丙基取代反应和分子内取代反应之中，能取代优秀的产率、区域选择性和对映选择性。可以应用在较复杂的底物上，极大的拓展了此类反应的使用范围。 

具体实施方式

通过下述实施例将有助于理解本发明，但并不限制本发明的内容。 

实施例1：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和相应不同的手性Feringa膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)。 

C-1: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

HR-MS(ESI+):计算值（calcd for）C₆₄H₅₂IrNO₂P[M⁺]:1090.3365,实测值 （found）:1090.3356. 

C-2: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-3: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H), 6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-4: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-5: 

浅黄色粉末,87%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),2.38(dd,J=11.1,4.5Hz,1H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),6.85-6.99(m,4H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.20-7.26(m,4H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

HR-MS(ESI+):calcd for C₆₆H₅₆IrNO₄P[M⁺]:1150.3576,found:1150.3569. 

C-6: 

浅黄色粉末,87%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),2.38(dd,J=11.1,4.5Hz,1H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),6.85-6.99(m,4H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.20-7.26(m,4H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-7: 

浅黄色粉末,87%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),2.38(dd,J=11.1,4.5Hz,1H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),6.85-6.99(m,4H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.20-7.26(m,4H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-8: 

浅黄色粉末,87%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),2.38(dd,J=11.1,4.5Hz,1H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),6.85-6.99(m,4H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.20-7.26(m,4H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J= 9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-9: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-10: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-11: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-12: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-13: 

MS(ESI+):1174(C₇₀H₆₄IrNO₂P[M⁺]) 

C-14: 

MS(ESI+):1174(C₇₀H₆₄IrNO₂P[M⁺]) 

C-15: 

MS(ESI+):1174(C₇₀H₆₄IrNO₂P[M⁺]) 

C-16: 

MS(ESI+):1174(C₇₀H₆₄IrNO₂P[M⁺]) 

C-17: 

MS(ESI+):1202(C₇₂H₆₈IrNO₂P[M⁺]) 

C-18: 

MS(ESI+):1202(C₇₂H₆₈IrNO₂P[M⁺]) 

C-19: 

MS(ESI+):1202(C₇₂H₆₈IrNO₂P[M⁺]) 

C-20: 

MS(ESI+):1202(C₇₂H₆₈IrNO₂P[M⁺]) 

C-21: 

MS(ESI+):1226(C₆₆H₅₀IrNO₂PF₆[M⁺]) 

C-22: 

MS(ESI+):1226(C₆₆H₅₀IrNO₂PF₆[M⁺]) 

C-23: 

MS(ESI+):1226(C₆₆H₅₀IrNO₂PF₆[M⁺]) 

C-24: 

MS(ESI+):1226(C₆₆H₅₀IrNO₂PF₆[M⁺]) 

C-25: 

MS(ESI+):1378(C₇₈H₅₈IrNO₂PF₆[M⁺]) 

C-26: 

MS(ESI+):1378(C₇₈H₅₈IrNO₂PF₆[M⁺]) 

C-27: 

MS(ESI+):1378(C₇₈H₅₈IrNO₂PF₆[M⁺]) 

C-28: 

MS(ESI+):1378(C₇₈H₅₈IrNO₂PF₆[M⁺]) 

C-29: 

MS(ESI+):1514(C₈₀H₅₆IrNO₂PF₁₂[M⁺]) 

C-30: 

MS(ESI+):1514(C₈₀H₅₆IrNO₂PF₁₂[M⁺]) 

C-31: 

MS(ESI+):1514(C₈₀H₅₆IrNO₂PF₁₂[M⁺]) 

C-32: 

MS(ESI+):1514(C₈₀H₅₆IrNO₂PF₁₂[M⁺]) 

C-33: 

MS(ESI+):1308(C₈₂H₅₄IrNO₂P[M⁺]) 

C-34: 

MS(ESI+):1308(C₈₂H₅₄IrNO₂P[M⁺]) 

C-35: 

MS(ESI+):1308(C₈₂H₅₄IrNO₂P[M⁺]) 

C-36: 

MS(ESI+):1308(C₈₂H₅₄IrNO₂P[M⁺]) 

C-37: 

MS(ESI+):1408(C₈₈H₈₂IrNO₂P[M⁺]) 

C-38: 

MS(ESI+):1408(C₈₈H₈₂IrNO₂P[M⁺]) 

C-39: 

MS(ESI+):1408(C₈₈H₈₂IrNO₂P[M⁺]) 

C-40: 

MS(ESI+):1408(C₈₈H₈₂IrNO₂P[M⁺]) 

C-41: 

MS(ESI+):1394(C₈₈H₆₈IrNO₂P[M⁺]) 

C-42: 

MS(ESI+):1394(C₈₈H₆₈IrNO₂P[M⁺]) 

C-43: 

MS(ESI+):1394(C₈₈H₆₈IrNO₂P[M⁺]) 

C-44: 

MS(ESI+):1394(C₈₈H₆₈IrNO₂P[M⁺]) 

C-45: 

MS(ESI+):1158(C₆₄H₅₀IrNO₂PCl₂[M⁺]) 

C-46: 

MS(ESI+):1158(C₆₄H₅₀IrNO₂PCl₂[M⁺]) 

C-47: 

MS(ESI+):1158(C₆₄H₅₀IrNO₂PCl₂[M⁺]) 

C-48: 

MS(ESI+):1246(C₆₄H₅₀IrNO₂PBr₂[M⁺]) 

C-49: 

MS(ESI+):1246(C₆₄H₅₀IrNO₂PBr₂[M⁺]) 

C-50: 

MS(ESI+):1246(C₆₄H₅₀IrNO₂PBr₂[M⁺]) 

C-51: 

MS(ESI+):1246(C₆₄H₅₀IrNO₂PBr₂[M⁺]) 

C-52: 

MS(ESI+):1246(C₆₄H₅₀IrNO₂PBr₂[M⁺]) 

C-53: 

MS(ESI+):1342(C₆₄H₅₀IrNO₂PI₂[M⁺]) 

C-54: 

MS(ESI+):1342(C₆₄H₅₀IrNO₂PI₂[M⁺]) 

C-55: 

MS(ESI+):1342(C₆₄H₅₀IrNO₂PI₂[M⁺]) 

C-56: 

MS(ESI+):1342(C₆₄H₅₀IrNO₂PI₂[M⁺]) 

C-57: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-58: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-59: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-60: 

MS(ESI+):1118(C₆₆H₅₆IrNO₂P[M⁺]) 

C-61: 

MS(ESI+):1242(C₇₆H₆₀IrNO₂P[M⁺]) 

C-62: 

MS(ESI+):1242(C₇₆H₆₀IrNO₂P[M⁺]) 

C-63: 

MS(ESI+):1242(C₇₆H₆₀IrNO₂P[M⁺]) 

C-64: 

MS(ESI+):1242(C₇₆H₆₀IrNO₂P[M⁺]) 

C-65: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,6H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-66: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,6H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-67: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,6H),7.18-7.22(m,4H), 7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-68: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,6H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-69: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H), 1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-70: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-71: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-72: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8 Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-73: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-74: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-75: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-76: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-77: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-78: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-79: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-80: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-81: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-82: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-83: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-84: 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺])。 

实施例2：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和相应不同的手性膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)，分别获得如下的络合物。 

C-85: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1098(C₆₄H₆₀IrNO₂P[M⁺]) 

C-86: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40 (m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1098(C₆₄H₆₀IrNO₂P[M⁺]) 

C-87: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1098(C₆₄H₆₀IrNO₂P[M⁺]) 

C-88: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz, 1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1098(C₆₄H₆₀IrNO₂P[M⁺]) 

C-89: 

浅黄色粉末,84%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),1.65-1.85(m,8H),2.38(dd,J=11.1,4.5Hz,1H),2.70-2.90(m,8H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1158(C₆₆H₆₄IrNO₄P[M⁺]) 

C-90: 

浅黄色粉末,84%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),1.65-1.85(m,8H),2.38(dd,J=11.1,4.5Hz,1H),2.70-2.90(m,8H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1158(C₆₆H₆₄IrNO₄P[M⁺]) 

C-91: 

浅黄色粉末,84%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),1.65-1.85(m,8H),2.38(dd,J=11.1,4.5Hz,1H),2.70-2.90(m,8H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1158(C₆₆H₆₄IrNO₄P[M⁺]) 

C-92: 

浅黄色粉末,84%yield,¹H NMR(300MHz,[d₈]-THF)δ0.46(d,J=7.5Hz,3H),0.97(t,J=11.1Hz,1H),1.64(dd,J=8.1,5.7Hz,3H),1.65-1.85(m,8H),2.38(dd,J=11.1,4.5Hz,1H),2.70-2.90(m,8H),2.94(d,J=10.5Hz,1H),3.24(t,J=6.9Hz,1H),3.55(s,3H),3.89(s,3H),4.40-4.67(m,5H),4.85(d,J=9.3Hz,1H),5.03(t,J=6.3Hz,1H),5.74(br,1H),6.37(d,J=8.1Hz,1H),6.43(d,J=8.7Hz,1H),6.49(t,J=8.4Hz,1H),6.80(t,J=6.9Hz,1H),7.04(t,J=7.5Hz,1H),7.08-7.16(m,2H),7.16-7.19(m,1H),7.26-7.31(m,2H),7.31-7.36(m,2H),7.40(t,J=7.2Hz,1H),7.51-7.63(m,6H),7.73(d,J=8.7Hz,1H),7.94(d,J=8.4Hz,1H),8.12(d,J=9.0Hz,1H),8.17(d,J=8.7Hz,1H),8.28(d,J=8.1Hz,1H),8.54(d,J=8.4Hz,1H). 

MS(ESI+):1158(C₆₆H₆₄IrNO₄P[M⁺]) 

C-93: 

MS(ESI+):1126(C₆₆H₆₄IrNO₂P[M⁺]) 

C-94: 

MS(ESI+):1126(C₆₆H₆₄IrNO₂P[M⁺]) 

C-95: 

MS(ESI+):1126(C₆₆H₆₄IrNO₂P[M⁺]) 

C-96: 

MS(ESI+):1126(C₆₆H₆₄IrNO₂P[M⁺]) 

C-97: 

MS(ESI+):1250(C₇₆H₆₈IrNO₂P[M⁺]) 

C-98: 

MS(ESI+):1250(C₇₆H₆₈IrNO₂P[M⁺]) 

C-99: 

MS(ESI+):1250(C₇₆H₆₈IrNO₂P[M⁺]) 

C-100: 

MS(ESI+):1250(C₇₆H₆₈IrNO₂P[M⁺]) 

C-101: 

浅黄色粉末,88%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1084(C₆₃H₅₈IrNO₂P[M⁺]) 

C-102: 

浅黄色粉末,88%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1084(C₆₃H₅₈IrNO₂P[M⁺]) 

C-103: 

浅黄色粉末,88%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4 Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1084(C₆₃H₅₈IrNO₂P[M⁺]) 

C-104: 

浅黄色粉末,88%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.65-1.85(m,8H),2.24(dd,J=11.0,5.6Hz,1H),2.70-2.90(m,8H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1084(C₆₃H₅₈IrNO₂P[M⁺]) 

C-105: 

MS(ESI+):1160(C₆₉H₆₂IrNO₂P[M⁺]) 

C-106: 

MS(ESI+):1160(C₆₉H₆₂IrNO₂P[M⁺]) 

C-107: 

MS(ESI+):1160(C₆₉H₆₂IrNO₂P[M⁺]) 

C-108: 

MS(ESI+):1160(C₆₉H₆₂IrNO₂P[M⁺])。 

实施例3：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和相应不同的手性膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)，分别获得如下络合物。 

C-109: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1078(C₅₈H₄₈IrNO₆P[M⁺]) 

C-110: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J= 8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1078(C₅₈H₄₈IrNO₆P[M⁺]) 

C-111: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1078(C₅₈H₄₈IrNO₆P[M⁺]) 

C-112: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H), 1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1078(C₅₈H₄₈IrNO₆P[M⁺]) 

C-113: 

MS(ESI+):1138(C₆₀H₅₂IrNO₈P[M⁺]) 

C-114: 

MS(ESI+):1138(C₆₀H₅₂IrNO₈P[M⁺]) 

C-115: 

MS(ESI+):1138(C₆₀H₅₂IrNO₈P[M⁺]) 

C-116: 

MS(ESI+):1138(C₆₀H₅₂IrNO₈P[M⁺]) 

C-117: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1064(C₅₇H₄₆IrNO₆P[M⁺]) 

C-118: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1064(C₅₇H₄₆IrNO₆P[M⁺]) 

C-119: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m, 1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1064(C₅₇H₄₆IrNO₆P[M⁺]) 

C-120: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.05(s,2H),6.08(s,2H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1064(C₅₇H₄₆IrNO₆P[M⁺]) 

C-121: 

MS(ESI+):1140(C₆₃H₆₀IrNO₆P[M⁺]) 

C-122: 

MS(ESI+):1140(C₆₃H₆₀IrNO₆P[M⁺]) 

C-123: 

MS(ESI+):1140(C₆₃H₆₀IrNO₆P[M⁺]) 

C-124: 

MS(ESI+):1140(C₆₃H₆₀IrNO₆P[M⁺])。 

实施例4：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和相应不同的手性膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)，分别获得如下络合物。 

C-125: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-126: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H), 6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-127: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-128: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1090(C₆₄H₅₂IrNO₂P[M⁺]) 

C-129: 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-130: 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-131: 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-132: 

MS(ESI+):1150(C₆₆H₅₆IrNO₄P[M⁺]) 

C-133: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-134: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-135: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz, 1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-136: 

浅黄色粉末,85%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1076(C₆₃H₅₀IrNO₂P[M⁺]) 

C-133: 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-134: 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-135: 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺]) 

C-136: 

MS(ESI+):1152(C₆₉H₅₄IrNO₂P[M⁺])。 

实施例5：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和相应的不同手性膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)，分别获得如下络合物。 

C-137: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1190(C₇₂H₅₆IrNO₂P[M⁺]) 

C-138: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1190(C₇₂H₅₆IrNO₂P[M⁺]) 

C-139: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H), 6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1190(C₇₂H₅₆IrNO₂P[M⁺]) 

C-140: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1190(C₇₂H₅₆IrNO₂P[M⁺]) 

C-141: 

MS(ESI+):1234(C₇₄H₆₀IrNO₄P[M⁺]) 

C-142: 

MS(ESI+):1234(C₇₄H₆₀IrNO₄P[M⁺]) 

C-143: 

MS(ESI+):1234(C₇₄H₆₀IrNO₄P[M⁺]) 

C-144: 

MS(ESI+):1234(C₇₄H₆₀IrNO₄P[M⁺]) 

C-145: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1176(C₇₁H₅₄IrNO₂P[M⁺]) 

C-146: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H), 7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1176(C₇₁H₅₄IrNO₂P[M⁺]) 

C-147: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1176(C₇₁H₅₄IrNO₂P[M⁺]) 

C-148: 

浅黄色粉末,80%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H), 1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.29-7.33(m,4H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.52-7.57(m,4H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1176(C₇₁H₅₄IrNO₂P[M⁺]) 

C-149: 

MS(ESI+):1252(C₇₇H₅₈IrNO₂P[M⁺]) 

C-150: 

MS(ESI+):1252(C₇₇H₅₈IrNO₂P[M⁺]) 

C-151: 

MS(ESI+):1252(C₇₇H₅₈IrNO₂P[M⁺]) 

C-152: 

MS(ESI+):1252(C₇₇H₅₈IrNO₂P[M⁺])。 

实施例6：具有二萘基[1,2-b;5,6-b’]环辛四烯和手性膦氮骨架的π-烯丙基铱络合物的合成： 

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(dncot)Cl]₂(2.1g,1.8mmol)和手性膦氮化合物(1.9g,3.6mmol)，100mL四氢呋喃（THF），室温（25°C）下搅拌反应1小时；然后依次加入AgOTf（460mg,1.8mmol）和巴豆碳酸酯（940mg,7.2mmol），该体系于室温（25°C）下避光搅拌24小时，砂芯漏斗过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(异丙醇/二氯甲烷:0:100->3/97)。 

C-153: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0 Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1056(C₆₁H₅₄IrNO₂P[M⁺]) 

C-154: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1056(C₆₁H₅₄IrNO₂P[M⁺]) 

C-155: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1056(C₆₁H₅₄IrNO₂P[M⁺]) 

C-156: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),1.60(dd,J=8.4,6.4Hz,3H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,1H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0 Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1056(C₆₁H₅₄IrNO₂P[M⁺]) 

C-157: 

MS(ESI+):1100(C₆₃H₅₈IrNO₄P[M⁺]) 

C-158: 

MS(ESI+):1100(C₆₃H₅₈IrNO₄P[M⁺]) 

C-159: 

MS(ESI+):1100(C₆₃H₅₈IrNO₄P[M⁺]) 

C-160: 

MS(ESI+):1100(C₆₃H₅₈IrNO₄P[M⁺]) 

C-161: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1070(C₆₀H₅₂IrNO₂P[M⁺]) 

C-162: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H), 1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1070(C₆₀H₅₂IrNO₂P[M⁺]) 

C-163: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1070(C₆₀H₅₂IrNO₂P[M⁺]) 

C-164: 

浅黄色粉末,81%yield,¹H NMR(400MHz,[d₈]-THF)δ0.59(d,J=7.2Hz,3H),1.21(t,J=12.0Hz,1H),2.24(dd,J=11.0,5.6Hz,1H),2.42-2.50(m,4H),2.75-2.85(m,4H),2.98(d,J=11.2Hz,2H),3.31(t,J=7.6Hz,1H),3.94(dd,J=16.4,7.2Hz,1H),4.02(dd,J=11.6,5.6Hz,1H),4.48(dd,J=9.2,2.8Hz,1H),4.50-4.59(m,2H),4.71-4.82(m,1H),4.85(d,J=9.2Hz,1H),5.21(dd,J=8.8,6.4Hz,1H),5.58(br,1H),6.32(dd,J=9.6,7.2Hz,1H),6.39(d,J=8.0Hz,1H),6.49(d,J=8.8Hz,1H),6.85(t,J=6.8Hz,1H),6.97(t,J=7.2Hz,1H),7.00(t,J=8.4Hz,1H),7.08-7.13(m,1H),7.18-7.22(m,4H),7.22-7.25(m,2H),7.36-7.40(m,2H),7.43-7.49(m,3H),7.59(d,J=7.6Hz,1H),7.65(t,J=7.2Hz,1H),7.79(d,J=8.8Hz,1H),7.90(d,J=8.0Hz,1H),7.95-8.05(m,4H),8.11(d,J=8.8Hz,1H),8.15(d,J=8.8Hz,1H),8.30(d,J=8.0Hz,1H),8.57(d,J=8.8Hz,1H). 

MS(ESI+):1070(C₆₀H₅₂IrNO₂P[M⁺]) 

C-165: 

MS(ESI+):1152(C₆₆H₅₆IrNO₂P[M⁺]) 

C-166: 

MS(ESI+):1152(C₆₆H₅₆IrNO₂P[M⁺]) 

C-167: 

MS(ESI+):1152(C₆₆H₅₆IrNO₂P[M⁺]) 

C-168: 

MS(ESI+):1152(C₆₆H₅₆IrNO₂P[M⁺])。 

该化合物的应用实施例7： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C1（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C1为催化剂)： 

无色油状液体,B/L>97:3,82%yield,94%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例8： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C2（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C2为催化剂)： 

无色油状液体,B/L>97:3,80%yield,94%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例9： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C3（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-2(使用络合物C3为催化剂)： 

无色油状液体,B/L>97:3,84%yield,94%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例10： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C4（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-2(使用络合物C4为催化剂)： 

无色油状液体,B/L>97:3,82%yield,94%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例11： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），相应不同的烯丙基碳酸酯（0.4mmol）和络合物C5（5.1mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定，分别获得如下产物。 

I-1(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,90%yield,98%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

I-3(使用络合物C5为催化剂)： 

无色油状液体，B/L＞97:3，88%yield，96%ee[Daicel Chiralcel OD-H，hexane/2-propanol=98/2，v=0.5ml min^-1，λ=230nm，t(minor)=12.63min，t(major)=16.40min];[α]_D^20.4=+0.8°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ 1.62(br,1H),3.70(s,2H),3.77(s,3H),4.17(d,J=7.2Hz,1H),5.11(d,J=9.6Hz,1H),5.19(d,J=17.1Hz,1H),5.92(ddd,J=17.1,9.9,7.2Hz,1H),6.81-6.91(m,2H),7.18-7.35(m,7H). 

I-4(使用络合物C5为催化剂)： 

无色油状液体，B/L＞97:3，93%yield，96%ee[Daicel Chiralcel OD-H，hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=13.30min,t(major)=17.83min];[α]_D^22.4=+3.8°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.62(br,1H),3.71(s,2H),3.77(s,3H),4.18(d,J=7.2Hz,1H),5.10(d,J=9.9Hz,1H),5.22(d,J=17.1Hz,1H),5.92(ddd,J=17.7,10.2,7.2Hz,1H),6.94-6.82(m,1H),6.91-6.98(m,2H),7.16-7.34(m,6H). 

I-5： 

无色油状液体，B/L＞97:3，95%yield，97%ee[Daicel Chiralcel OD-H，hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=10.50min,t(major)=11.92min];[α]_D^24.1=-1.5°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.59(br,1H),3.66(AB,J_AB=13.8Hz,1H),3.71(BA,J_BA=13.5Hz,1H),4.17(d,J=7.2Hz,1H),5.11(d,J=9.3Hz,1H),5.20(d,J=17.1Hz,1H),5.87(ddd,J=16.8,9.6,6.9Hz,1H),7.19-7.36(m,7H),7.40-7.50(m,2H). 

I-6(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,81:oyield,95:oee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=10.27min,t(major)=11.55min];[α]_D^23.3=+0.1°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.60(br,1H),3.67(AB,J_AB=13.8Hz,1H),3.72(BA,J_BA=13.8Hz,1H),4.19(d,J=7.2Hz,1H),5.12(d,J=9.9Hz,1H),5.20(d,J=17.1Hz,1H),5.88(ddd,J=17.1,9.9,6.9Hz,1H),7.20-7.36(m,9H). 

I-7(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,68%yield,96%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=17.97min,t(major)=19.74min];[α]_D^23.4=+2.8°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.35(br,1H),1.63-1.92(m,2H),2.50-2.73(m,2H),2.99-3.11(m,1H),3.62(AB,J_AB=13.5Hz,1H),3.82(BA,J_BA=13.2Hz,1H),5.14(d,J=18.0Hz,1H),5.19(d,J=12.0Hz,1H),5.57-5.77(m,1H),7.09-7.19(m,3H),7.20-7.35(m,7H). 

I-8(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,89%yield,82%ee[Daicel Chiralpak AD-H,hexane/2-propanol=90/10,v=0.5ml min^-1,λ=210nm,t(minor)=7.20min,t(major)=8.85min];[α]_D^22.0=+34.2°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.04(s,9H),2.18(br,1H),2.50-2.73(m,1H),3.63(d,J=6.0Hz,2H),3.66(d,J=14.7Hz,1H),3.89(d,J=13.8Hz,1H),5.15(d,J=9.9Hz,1H),5.16(d,J=18.6Hz,1H),5.62(ddd,J=18.0,9.9,7.8Hz,1H),7.19-7.46(m,11H),7.57-7.68(m,4H). 

该化合物的应用实施例12： 

一般反应操作：无需氩气保护，敞口反应，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C5（5.1mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,89%yield,98%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例12： 

一般反应操作：氩气保护下，往Schlenk管中加入NaCH(CO₂Me)₂（0.8mmol），相应不同的烯丙基碳酸酯（0.4mmol）和络合物C5（5.1mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应1-4小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-9(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,yield91%,98%ee[Daicel Chiralcel OJ-H,hexane/2-propanol=95/5,v=1.0ml min^-1,λ=230nm,t(minor)=24.71min,t (major)=27.16min];[α]_D^23.1=+31.1°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ3.48(s,3H),3.73(s,3H),3.87(d,J=11.1Hz,1H),4.10(dd,J=10.5,8.7Hz,1H),5.08(d,J=9.6Hz,1H),5.12(d,J=16.5Hz,1H),5.99(ddd,J=18.0,9.3,8.1Hz,1H),7.15-7.24(m,3H),7.25-7.33(m,2H). 

I-10(使用络合物C5为催化剂)： 

无色油状液体,B/L=94:6,79%yield,84%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm，t(major)=10.l5min，t(minor)=11.17min];[α]_D^18.0=+42.5°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.05(s,9H),2.96-3.10(m,1H),3.67(s,3H),3.69(s,3H),3.69-3.76(m,2H),3.88(d,J=8.1Hz,1H),5.10(d,J=10.2Hz,1H),5.11(d,J=17.7Hz,1H),5.90(dt,J=16.8,9.3Hz,1H),7.32-7.46(m,6H),7.57-7.66(m,4H). 

I-11(使用络合物C5为催化剂)： 

无色油状液体,B/L=93:7,79%yield,84%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm，t(major)=10.l5min，t(minor)=11.17min];[α]_D^18.0=+42.5°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.05(s,9H),2.96-3.10(m,1H),3.67(s,3H),3.69(s,3H),3.69-3.76(m,2H),3.88(d,J=8.1Hz,1H),5.10(d,J=10.2Hz,1H),5.11(d,J=17.7Hz,1H),5.90(dt,J=16.8,9.3Hz,1H),7.32-7.46(m,6H),7.57-7.66(m,4H). 

I-12(使用络合物C5为催化剂)： 

无色油状液体,B/L=94:6,89%yield,84%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm，t(major)=14.79min，t(minor)=17.21min];[α]_D^23.3=+29.4°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ3.03-3.15(m,1H),3.15-3.24(m,2H),3.56(s,3H),3.62(s,3H),3.82(d,J=8.1Hz,1H),5.10(d,J=9.9Hz,1H),5.11(d,J=18.9Hz,1H),5.91(dt,J=17.1,9.9Hz,1H),7.15-7.32(m,9H),7.35-7.47(m,6H). 

I-13(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,82%yield,95%ee[Daicel Chiralpak AD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(major)=12.72min,t(minor)=13.61min];[α]_D^22.2=-2.3°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.51-3.68(m,1H),1.78-1.92(m,1H),2.92-3.06(m,2H),3.07-3.17(m,1H),3.42(d,J=8.4Hz,1H),3.66(s,3H),3.72(s,3H),4.92(d,J=9.0Hz,1H),4.94(d,J=17.1Hz,1H),5.55(dt,J=17.1,9.6Hz,1H),7.15-7.31(m,9H),7.38-7.46(m,6H). 

该化合物的应用实施例13： 

一般反应操作：氩气保护下，往Schlenk管中加入NaCH(CO₂Me)₂（1.6mmol），烯丙基碳酸酯（153.6mg,0.8mmol）和络合物C5（1.0mg,0.1mol%）于2.0mL四氢呋喃（THF）中，50℃下搅拌反应4小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-9(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,86%yield,98%ee[Daicel Chiralcel OJ-H,hexane/2-propanol=95/5,v=1.0ml min^-1,λ=230nm,t(minor)=24.71min,t(major)=27.16min];[α]_D^23.1=+31.1°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ3.48(s,3H),3.73(s,3H),3.87(d,J=11.1Hz,1H),4.10(dd,J=10.5,8.7Hz,1H),5.08(d,J=9.6Hz,1H),5.12(d,J=16.5Hz,1H),5.99(ddd,J=18.0,9.3,8.1Hz,1H),7.15-7.24(m,3H),7.25-7.33(m,2H). 

该化合物的应用实施例14： 

一般反应操作：氩气保护下，往Schlenk管中加入NaCH(CO₂Me)₂（16mmol），烯丙基碳酸酯（1.54g,8mmol）和络合物C5（1.0mg,0.01mol%）于20mL四氢呋喃（THF）中，50℃下搅拌反应48小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-9(使用络合物C5为催化剂)： 

无色油状液体,B/L>97:3,52%yield,98%ee[Daicel Chiralcel OJ-H,hexane/2-propanol=95/5,v=1.0ml min^-1,λ=230nm,t(minor)=24.71min,t(major)=27.16min];[α]_D^23.1=+31.1°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ3.48(s,3H),3.73(s,3H),3.87(d,J=11.1Hz,1H),4.10(dd,J=10.5,8.7Hz,1H),5.08(d,J=9.6Hz,1H),5.12(d,J=16.5Hz,1H),5.99(ddd,J=18.0,9.3,8.1Hz,1H),7.15-7.24(m,3H),7.25-7.33(m,2H). 

该化合物的应用实施例15： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C65（4.6mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C65为催化剂)： 

无色油状液体,B/L>97:3,85%yield,96%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例16： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C69（4.3mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C69为催化剂)： 

无色油状液体,B/L>97:3,83%yield,97%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例17： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C85（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C85为催化剂)： 

无色油状液体,B/L>97:3,89%yield,97%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例18： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C101（4.3mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C101为催化剂)： 

无色油状液体,B/L>97:3,83%yield,95%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例19： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C109（4.3mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C109为催化剂)： 

无色油状液体,B/L>97:3,86%yield,96%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例20： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C117（4.2mg,1mol%）于1.0mL四氢呋 喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C117为催化剂)： 

无色油状液体,B/L>97:3,82%yield,96%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例21： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C125（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C125为催化剂)： 

无色油状液体,B/L>97:3,86%yield,96%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ 1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例22： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C133（4.4mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C133为催化剂)： 

无色油状液体,B/L>97:3,89%yield,94%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例23： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C153（4.2mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-1(使用络合物C153为催化剂)： 

无色油状液体,B/L>97:3,88%yield,98%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例24： 

一般反应操作：氩气保护下，往Schlenk管中加入苄胺（85.6mg,0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C161（4.1mg,1mol%）于1.0mL四氢呋 喃（THF）中，50℃下搅拌反应24小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。I-1(使用络合物C161为催化剂)： 

无色油状液体,B/L>97:3,81%yield,98%ee[Daicel Chiralcel OD-H,hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(minor)=9.31min,t(major)=10.25min];[α]_D^18.2=+6.2°(c1.00,CHCl₃).¹H NMR(400MHz,CDCl₃)δ1.66(br,1H),3.70(AB,J_AB=13.2Hz,1H),3.74(BA,J_BA=13.2Hz,1H),4.22(d,J=7.2Hz,1H),5.11(d,J=10.0Hz,1H),5.22(d,J=17.2Hz,1H),5.94(ddd,J=17.2,10.4,7.2Hz,1H),7.19-7.27(m,2H),7.29-7.39(m,8H). 

该化合物的应用实施例25： 

一般反应操作：氩气保护下，往Schlenk管中加入NaCH(CO₂Me)₂（0.8mmol），烯丙基碳酸酯（0.4mmol）和络合物C5（4.1mg,1mol%）于1.0mL四氢呋喃（THF）中，50℃下搅拌反应1-4小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯=20/1)。产物的ee由HPLC测定。 

I-9(使用络合物C161为催化剂)： 

无色油状液体,B/L>97:3,yield95%,98%ee[Daicel Chiralcel OJ-H,hexane/2-propanol=95/5,v=1.0ml min^-1,λ=230nm,t(minor)=24.71min,t(major)=27.16min];[α]_D^23.1=+31.1°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ 3.48(s,3H),3.73(s,3H),3.87(d,J=11.1Hz,1H),4.10(dd,J=10.5,8.7Hz,1H),5.08(d,J=9.6Hz,1H),5.12(d,J=16.5Hz,1H),5.99(ddd,J=18.0,9.3,8.1Hz,1H),7.15-7.24(m,3H),7.25-7.33(m,2H). 

I-10(使用络合物C161为催化剂)： 

无色油状液体,B/L=94:6,79%yield,87%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm，t(major)=10.l5min，t(minor)=11.17min];[α]_D^18.0=+42.5°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.05(s,9H),2.96-3.10(m,1H),3.67(s,3H),3.69(s,3H),3.69-3.76(m,2H),3.88(d,J=8.1Hz,1H),5.10(d,J=10.2Hz,1H),5.11(d,J=17.7Hz,1H),5.90(dt,J=16.8,9.3Hz,1H),7.32-7.46(m,6H),7.57-7.66(m,4H). 

I-11(使用络合物C61为催化剂)： 

无色油状液体,B/L=93:7,72%yield,89%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1,λ=230nm，t(major)=10.l5min，t(minor)=11.17min];[α]_D^18.0=+42.5°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.05(s,9H),2.96-3.10(m,1H),3.67(s,3H),3.69(s,3H),3.69-3.76(m,2H),3.88(d,J=8.1Hz,1H),5.10(d,J=10.2Hz,1H),5.11(d,J=17.7Hz,1H),5.90(dt,J=16.8,9.3Hz,1H),7.32-7.46(m,6H),7.57-7.66(m,4H). 

I-12(使用络合物C61为催化剂)： 

无色油状液体,B/L=94:6,89%yield,84%ee[Daicel Chiralpak AD-H,hexane/2-propano1=98/2,v=0.5ml min^-1)λ=230nm，t(major)=14.79min，t(minor)=17.21min];[α]_D^23.3=+29.4°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ3.03-3.15(m,1H),3.15-3.24(m,2H),3.56(s,3H),3.62(s,3H),3.82(d,J=8.1Hz,1H),5.10(d,J=9.9Hz,1H),5.11(d,J=18.9Hz,1H),5.91(dt,J=17.1,9.9Hz,1H),7.15-7.32(m,9H),7.35-7.47(m,6H). 

I-13(使用络合物C161为催化剂)： 

无色油状液体,B/L>97:3,87%yield,92%ee[Daicel Chiralpak AD-H, hexane/2-propanol=98/2,v=0.5ml min^-1,λ=230nm,t(major)=12.72min,t(minor)=13.61min];[α]_D^22.2=-2.3°(c1.00,CHCl₃).¹H NMR(300MHz,CDCl₃)δ1.51-3.68(m,1H),1.78-1.92(m,1H),2.92-3.06(m,2H),3.07-3.17(m,1H),3.42(d,J=8.4Hz,1H),3.66(s,3H),3.72(s,3H),4.92(d,J=9.0Hz,1H),4.94(d,J=17.1Hz,1H),5.55(dt,J=17.1,9.6Hz,1H),7.15-7.31(m,9H),7.38-7.46(m,6H)。