CN103087106A - 含有n－芳基的手性膦氮类化合物、合成方法以及应用 - Google Patents

含有n－芳基的手性膦氮类化合物、合成方法以及应用 Download PDF

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CN103087106A
CN103087106A CN2013100401040A CN201310040104A CN103087106A CN 103087106 A CN103087106 A CN 103087106A CN 2013100401040 A CN2013100401040 A CN 2013100401040A CN 201310040104 A CN201310040104 A CN 201310040104A CN 103087106 A CN103087106 A CN 103087106A
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maldi
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CN103087106B (zh
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游书力
卓春祥
刘文博
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

本发明提供了一种含有N-芳基膦氮类化合物、其合成方法和应用。该膦氮化合物基于轴手性或者含有螺手性骨架，是以光学纯的轴手性或者螺手性二醇类化合物、三氯化磷和芳香二级胺为原料进行反应合成，该方法的原料易得、反应条件温和、产物易于分离提纯。本发明所合成的基于轴手性或者螺手性骨架的N-芳基膦氮类化合物，可以有效的应用于金属铱催化的烯丙基取代反应中，能以高的对映选择性和区域选择性得到产物，极大地拓宽了此类反应的底物范围。

Description

含有N-芳基的手性膦氮类化合物、合成方法以及应用
技术领域
本发明涉及基于轴手性或者螺手性骨架的N－芳基膦氮类化合物、合成方法及应用，该方法可以高收率的合成这种配体，并把该配体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。目前此类反应的配体主要是Ferringa配体及其衍生物[(a)Feringa,B.L.Acc.Chem.Res.2000,33,346.(b)Alexakis,A.;Rosset,S.;Allamand,J.;March,S.;Guillen,F.;Benhaim,C.Synlett2001,1375-1378.(c)Naasz,R.;Arnold,L.A.;Minnaard,A.J.;Feringa,B.L.Angew.Chem.Int.Ed.2001,40,927-930.(d)Polet,D.;Alexakis,A.Synthesis 2004,2586-2590.(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.]。而这类配体合成比较复杂，尽管已经商业化，但是价格非常昂贵，更重要的是其本身具有很大的局限性，底物的普适性并不是很好。比如对邻位取代的肉桂碳酸酯底物的对映选择性控制较差[(a)López,F.;Ohmura,T.;Hartwig,J.F.J. Am.Chem.Soc.2003,125,3426.(b)Polet,D.;Alexakis,A.;Tissot-Croset,K.;Corminboeuf，C.;Ditrich,K.Chem.Eur.J.2006,12,3596.(c)Yamashita,Y.;Gopalarathnam,A.;Hartwig,J.F.J.Am.Chem.Soc.2007,129,7508.(d)Pouy,M.J.;Leitner,A.;Weix,D.J.;Ueno,S.;Hartwig,J.F.Org.Lett.2007,9,3949.(e)Liu,W.-B.;He,H.;Dai,L.-X.;You,S.-L.Org.Lett.2008,10,1815.(f)Liu,W.-B.;Zheng,C.;Zhuo,C.-X.;Dai,L.-X.;You,S.-L.J.Am.Chem.Soc.2012,134,4812.]；以及对分子内烯丙基取代反应的非对映选择性控制也比较差[(a)Wu,Q.-F.;He,H.;Liu,W.-B.;You,S.-L.J.Am.Chem.Soc.2010,132,11418.(b)Zhuo,C.-X.;Liu,W.-B.;Wu,Q.-F.;You,S.-L.Chem.Sci.2012,3,205.]。为了解决这些问题，我们设计合成了一系列基于轴手性或者螺手性骨架的N－芳基膦氮类配体，该配体合成简单，容易通过重结晶提纯，并且对金属铱催化的烯丙基取代反应具有非常好的效果。尤其是对于复杂的底物，该配体通常能取得非常好的对映选择性和非对映选择性。因此该配体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N-芳基膦氮类化合物、合成方法和这种化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轴手性或者螺手性骨架二酚、三氯化磷和取代的芳香二级胺化合物合成膦氮类化合物的方法。
本发明的方法是一种有效的以光学纯的轴手性或者螺手性骨架二酚，三氯化磷，非手性的芳香二级胺或者光学纯的芳香二级胺化合物为原料的合成基于轴手性或者螺手性二酚骨架的N-芳基膦氮类化合物的方法。
本发明所合成的光学纯N-芳基膦氮类化合物可以应用在金属铱催化的不对称烯丙基取代反应中，能以高的效率和对映选择性得到产物。
本发明所述的N－芳基的膦氮类化合物的结构式是：
Figure BDA00002801739700021
或者其（非）对映异构体
Figure BDA00002801739700022
Figure BDA00002801739700023
或者其（非）对映异构体
Figure BDA00002801739700024
Figure BDA00002801739700025
或者其（非）对映异构体
Figure BDA00002801739700026
Figure BDA00002801739700031
或者其（非）对映异构体
Figure BDA00002801739700032
Figure BDA00002801739700033
或者其（非）对映异构体
Figure BDA00002801739700035
或者其（非）对映异构体
Figure BDA00002801739700036
的光学纯化合物；其中R1,R2,R3,R4为氢原子、含1-6个碳原子的烷基、含1-6个碳原子的全氟烷基、含1-6个碳原子的烷氧基、或者为卤素、含6-16个碳的芳基；其中R5、R6、R7为氢原子、卤素、含1-4个碳的烷基、含1-4个碳的环烷基、或者含1-4个碳的全氟烷基，苯基或者萘基；Ar1,Ar2为取代的苯基，萘基或者蒽基；n为1、2或者3。
本发明所述的N-芳基膦氮化合物是以轴手性或者螺手性二酚、三氯化磷和非手性芳香二级胺或者光学纯芳香二级胺为原料，在有机溶剂和碱的作用下反应制得，根据具体结构，可分别用以下方程式1-12表示：
方程式1：
Figure BDA00002801739700037
方程式2：
方程式3：
方程式4：
Figure BDA00002801739700043
方程式5：
Figure BDA00002801739700044
方程式6：
Figure BDA00002801739700045
方程式7：
Figure BDA00002801739700046
方程式8：
Figure BDA00002801739700051
方程式9：
Figure BDA00002801739700052
方程式10：
Figure BDA00002801739700053
方程式11：
Figure BDA00002801739700054
方程式12：
Figure BDA00002801739700055
以上方程式中，base表示碱，solvents表示有机溶剂；其中R1,R2,R3,R4为氢原子、含1-6个碳原子的烷基、含1-6个碳原子的全氟烷基、含1-6个碳原子的烷氧基、或者为卤素、含6-16个碳的芳基；其中R5、R6、R7为氢原子、卤素、含1-4个碳的烷基、含1-4个碳的环烷基、或者含1-4个碳的全氟烷基，苯基或者萘基；Ar1,Ar2为取代的苯基，萘基或者蒽基；n为1、2或者3。
所述的碱(base)是三乙胺、二异丙基乙基胺、氢化钠、正丁基锂、二（三甲基硅基）氨基钠、二（三甲基硅基）氨基锂、或者二（三甲基硅基）氨基钾。
所述的二酚类化合物、芳香二级胺、三氯化磷、碱的摩尔比为1-1.5:1-1.5:1-1.5:3-10，推荐反应的摩尔比为：二酚类化合物、芳香二级胺、三氯化磷、碱的摩尔比为1:1:1:6。反应在温度为-78℃至120℃，推荐反应温度为：0℃至80℃。反应时间为8小时－24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，推荐溶剂为甲苯和四氢呋喃。
采用本发明方法所得的产物N-芳基膦氮类化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，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轴手性或者螺手性二酚类化合物、芳基胺类化合物和三氯化磷为原料合成基于轴手性或螺手性骨架的膦氮类化合物的方法。该方法反应条件温和，操作简单原料易得，收率高，提纯方便。
本发明所提供的基于轴手性和螺手性骨架的N-芳基膦氮类化合物，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、对映选择性和非对映选择性。可以应用再较复杂的底物上，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：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700071
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(50mL)和三苯基膦(0.67mL,7.7mmol)，冷却至0°C；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(7.7mmol),甲苯(8mL),和三乙胺(1.8mL,12.9mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入联萘二酚（BINOL）(7.0mmol)和三乙胺(3.5mL,25.2mmol)的甲苯(30mL)和四氢呋喃(6mL)溶液。该体系于室温（25°C）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:10/1/0.01)。
I-1:
Figure BDA00002801739700072
白色固体,61%产率(yield),mp:204-205℃,[α]D 20=-242.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).13C NMR(75MHz,CDCl3)δ149.81(d,J=7.8Hz),148.8,143.3,143.2,141.5,141.5,140.7,140.6,132.75(d,J=1.7Hz),132.27(d,J=1.7Hz),131.37(d,J=1.1Hz),130.28(d,J=1.1Hz),130.2,129.52(d,J=2.3Hz),129.46(d,J=1.7Hz),129.1,128.7,128.66,128.6,128.3,128.2,128.1,128.0,127.9,127.4,127.3,127.2,127.06,126.9,126.0,125.6,125.4,124.8,124.3,124.23(d,J=5.1Hz),122.12(d,J=2.2Hz),121.9,121.18(d,J=2.8Hz),67.91(d,J=17.6Hz).31P NMR(121MHz,CDCl3)δ141.6.IR(液模liquidfilm):νmax(cm-1)=3061,1618,1589,1486,1463,1147,1431,1368,1327,1230,1214,1177,1154,1073,1047,1028,1001,981,946,920,820,802,778,746,701,691.MS(MALDI):484[M+H]+.HRMS(MALDI)计算值（calcd for）C39H29NO2P[M+H]+:574.1930.实测值（Found）:574.1935.
I-2:
白色固体,61%yield,mp:204-205℃,[α]D 20=+242.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):484[M+H]+.
I-3:
Figure BDA00002801739700082
白色固体,65%yield,mp:212-215℃,[α]D 20=-210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).2.26(s,6H).MS(MALDI):602[M+H]+.
I-4:
白色固体,65%yield,mp:214-216℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),2.26(s,6H).MS(MALDI):602[M+H]+.
I-5:
MS(MALDI):658[M+H]++.
I-6:
Figure BDA00002801739700092
MS(MALDI):602[M+H]+.
I-7:
Figure BDA00002801739700093
MS(MALDI):686[M+H]+.
I-8:
Figure BDA00002801739700094
MS(MALDI):686[M+H]+.
I-9:
Figure BDA00002801739700095
白色固体,52%yield,mp:210-215℃,[α]D 20=-198.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):710[M+H]+.
I-10:
Figure BDA00002801739700101
MS(MALDI):710[M+H]+.
I-11:
Figure BDA00002801739700102
白色固体,70%yield,mp:230-235℃,[α]D 20=-220.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,13H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):726[M+H]+.
I-12:
Figure BDA00002801739700103
MS(MALDI):726[M+H]+.
I-13：
Figure BDA00002801739700104
MS(MALDI):862[M+H]+.
I-14：
Figure BDA00002801739700111
MS(MALDI):862[M+H]+.
I-15：
Figure BDA00002801739700112
MS(MALDI):998[M+H]+.
I-16：
Figure BDA00002801739700113
MS(MALDI):998[M+H]+.
I-17：
Figure BDA00002801739700114
白色固体,65%yield,mp:214-216℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.05(s,4H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),2.26(s,18H).MS(MALDI):810[M+H]+.
I-18：
MS(MALDI):810[M+H]+.
I-19:
MS(MALDI):894[M+H]+.I-20:
Figure BDA00002801739700122
MS(MALDI):894[M+H]+.I-21:
Figure BDA00002801739700123
MS(MALDI):878[M+H]+.
I-22:
Figure BDA00002801739700124
MS(MALDI):878[M+H]+.
I-23:
Figure BDA00002801739700125
MS(MALDI):642[M+H]+.
I-24:
Figure BDA00002801739700131
MS(MALDI):642[M+H]+.
I-25:
白色固体,72%yield,mp:210-215℃,[α]D 20=-218.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):730[M+H]+.
I-26:
Figure BDA00002801739700133
MS(MALDI):730[M+H]+.
I-27:
Figure BDA00002801739700134
MS(MALDI):826[M+H]+.
I-28:
Figure BDA00002801739700135
MS(MALDI):826[M+H]+.
I-29:
Figure BDA00002801739700141
白色固体,75%yield,mp:220-222℃,[α]D 20=-215.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).2.45(s,6H).MS(MALDI):602[M+H]+.
I-30:
Figure BDA00002801739700142
MS(MALDI):602[M+H]+.
I-31:
Figure BDA00002801739700143
MS(MALDI):726[M+H]+.
I-32:
Figure BDA00002801739700144
MS(MALDI):726[M+H]+.
I-33:
Figure BDA00002801739700145
白色固体,65%yield,mp:210-215℃,[α]D 20=-215.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,4H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).3.83(s,3H).MS(MALDI):604[M+H]+.
I-34:
MS(MALDI):604[M+H]+.
I-35:
MS(MALDI):604[M+H]+.
I-36:
Figure BDA00002801739700153
MS(MALDI):604[M+H]+.
I-37:
Figure BDA00002801739700154
白色固体,60%yield,mp:213-217℃,[α]D 20=-216.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,4H),6.77(d,J=8.7Hz,1H),6.12(d,J=9.0Hz,1H).MS(MALDI):642[M+H]+.
I-38:
Figure BDA00002801739700155
MS(MALDI):642[M+H]+.
I-39：
Figure BDA00002801739700161
MS(MALDI):642[M+H]+.
I-40：
Figure BDA00002801739700162
MS(MALDI):642[M+H]+.
I-41：
Figure BDA00002801739700163
MS(MALDI):624[M+H]+.
I-42:
MS(MALDI):624[M+H]+.
I-43:
Figure BDA00002801739700165
白色固体,57%yield,mp:232-235℃,[α]D 20=-219.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,20H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):624[M+H]+.
I-44:
Figure BDA00002801739700171
MS(MALDI):624[M+H]+.
I-45:
Figure BDA00002801739700172
白色固体,65%yield,mp:214-218℃,[α]D 20=-202.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):572[M+H]+.
I-46:
MS(MALDI):572[M+H]+.
I-47:
Figure BDA00002801739700174
白色固体,67%yield,mp:212-215℃,[α]D 20=-230.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):588[M+H]+.
I-48:
Figure BDA00002801739700181
MS(MALDI):588[M+H]+.
实施例2：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700182
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(50mL)和三苯基膦(0.67mL,7.7mmol)，冷却至0°C；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(7.7mmol),甲苯(8mL),和三乙胺(1.8mL,12.9mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚2(7.0mmol)和三乙胺(3.5mL,25.2mmol)的甲苯(30mL)和四氢呋喃(6mL)溶液。该体系于室温（25°C）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:20/1/0.01)。
I-49:
Figure BDA00002801739700183
白色固体,55%yield,mp:198-199℃,[α]D 20=-145.3(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),2.74-2.83(m,8H),1.75-1.62(m,8H).MS(MALDI):582[M+H]+.
I-50:
Figure BDA00002801739700191
白色固体,55%yield,mp:198-199℃,[α]D 20=+145.3(c1.0,CHCl3).1HNMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),2.74-2.83(m,8H),1.75-1.62(m,8H).MS(MALDI):582[M+H]+.
I-51:
Figure BDA00002801739700192
MS(MALDI):642[M+H]+.
I-52:
Figure BDA00002801739700193
MS(MALDI):642[M+H]+.
I-53:
Figure BDA00002801739700194
MS(MALDI):734[M+H]+.
I-54:
MS(MALDI):734[M+H]+.
实施例3：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700201
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(50mL)和三苯基膦(0.67mL,7.7mmol)，冷却至0℃；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(7.7mmol),甲苯(8mL),和三乙胺(1.8mL,12.9mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80°C反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚3(7.0mmol)和三乙胺(3.5mL,25.2mmol)的甲苯(30mL)和四氢呋喃(6mL)溶液。该体系于室温（25℃）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:5/1/0.01)。
I-55:
白色固体,68%yield,mp:178-179℃,[α]D 20=-196.3(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),6.05(s,4H).MS(MALDI):562[M+H]+.
I-56:
Figure BDA00002801739700203
白色固体,68%yield,mp:178-179℃,[α]D 20=-196.3(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),6.05(s,4H).MS(MALDI):562[M+H]+.
I-57
Figure BDA00002801739700211
MS(MALDI):590[M+H]+.
I-58:
Figure BDA00002801739700212
MS(MALDI):590[M+H]+.
I-59:
Figure BDA00002801739700213
MS(MALDI):713[M+H]+.
I-60:
Figure BDA00002801739700214
MS(MALDI):713[M+H]+.
实施例4：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700215
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(25mL)和三苯基膦(0.33mL,3.9mmol)，冷却至0℃；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(3.9mmol),甲苯(4mL),和三乙胺(0.9mL,6.5mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚4(3.5mmol)和三乙胺(1.7mL,12.6mmol)的甲苯(15mL)和四氢呋喃(3mL)溶液。该体系于室温（25℃）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:8/1/0.01)。
I-61:
Figure BDA00002801739700221
白色固体,68%yield,mp:188-189℃,[α]D 20=-199.3(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),6.05(s,4H),4.50(t,J=10.2Hz,4H),4.20(t,J=10.2Hz,4H).MS(MALDI):590[M+H]+.
I-62:
Figure BDA00002801739700222
白色固体,68%yield,mp:188-189℃,[α]D 20=+199.3(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,10H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),6.05(s,4H),4.50(t,J=10.2Hz,4H),4.20(t,J=10.2Hz,4H).MS(MALDI):590[M+H]+.
I-63:
Figure BDA00002801739700223
MS(MALDI):618[M+H]+.
I-64:
Figure BDA00002801739700231
MS(MALDI):618[M+H]+.
I-65:
Figure BDA00002801739700232
MS(MALDI):742[M+H]+.
I-66:
Figure BDA00002801739700233
MS(MALDI):742[M+H]+.
实施例5：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700234
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(25mL)和三苯基膦(0.33mL,3.9mmol)，冷却至0℃；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(3.9mmol),甲苯(4mL),和三乙胺(0.9mL,6.5mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚5(3.5mmol)和三乙胺(1.7mL,12.6mmol)的甲苯(15mL)和四氢呋喃(3mL)溶液。该体系于室温（25°C）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:20/1/0.01)。
I-67:
Figure BDA00002801739700241
白色固体,73%yield,mp:205-206℃,[α]D 20=-233.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ8.22(d,J=8.7Hz,2H),8.02(d,J=9.3Hz,2H),7.46-7.17(m,22H),7.03-6.87(m,8H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):726[M+H]+.
I-68:
Figure BDA00002801739700242
白色固体,73%yield,mp:205-206℃,[α]D 20=+233.5(c1.0,CHCl3).1HNMR(300MHz,CDCl3)δ8.22(d,J=8.7Hz,2H),8.02(d,J=9.3Hz,2H),7.46-7.17(m,22H),7.03-6.87(m,8H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):726[M+H]+.
I-69:
Figure BDA00002801739700243
MS(MALDI):754[M+H]+.
I-70:
Figure BDA00002801739700251
MS(MALDI):754[M+H]+.
实施例6：基于轴手性N-芳基膦氮类化合物的合成：
Figure BDA00002801739700252
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(25mL)和三苯基膦(0.33mL,3.9mmol)，冷却至0℃；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(3.9mmol),甲苯(4mL),和三乙胺(0.9mL,6.5mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚6(3.5mmol)和三乙胺(1.7mL,12.6mmol)的甲苯(15mL)和四氢呋喃(3mL)溶液。该体系于室温（25°C）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:20/1/0.01)。
I-71:
Figure BDA00002801739700253
白色固体,75%yield,mp:216-217℃,[α]D 20=-254.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ8.42(d,J=8.7Hz,2H),8.12(d,J=9.3Hz,2H),7.46-7.17(m,24H),7.03-6.87(m,10H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):826[M+H]+.
I-72:
Figure BDA00002801739700261
白色固体,75%yield,mp:216-217℃,[α]D 20=-254.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ8.42(d,J=8.7Hz,2H),8.12(d,J=9.3Hz,2H),7.46-7.17(m,24H),7.03-6.87(m,10H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):826[M+H]+.
实施例7：基于轴手性N-芳基膦氮类化合物的合成：
氩气保护下，在一个干燥的250毫升三口瓶中，加入甲苯（toluene）(50mL)和三苯基膦(0.67mL,7.7mmol)，冷却至0℃；在另一个干燥的25毫升烧瓶中，加入芳香二级胺(7.7mmol),甲苯(8mL),和三乙胺(1.8mL,12.9mmol)，制成混合溶液，然后把该混合溶液逐渐滴加到上述250毫升的烧瓶中。滴加完毕后，升温至80℃反应6小时，然后再逐渐冷却至0℃。再向该体系中缓慢加入二酚7(7.0mmol)和三乙胺(3.5mL,25.2mmol)的甲苯(30mL)和四氢呋喃(6mL)溶液。该体系于室温（25℃）下搅拌过夜，硅藻土过滤，减压蒸馏除去溶剂，粗产物通过柱层析分离(石油醚/乙酸乙酯/三乙胺:5/1/0.01)。。
I-73:
Figure BDA00002801739700271
白色固体,83%yield,mp:233-235℃,[α]D 20=-209.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,9H),7.18-7.10(m,3H),7.01-6.89(m,5H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,2H),1.92-1.86(m,2H).MS(MALDI):540[M+H]+.
I-74:
白色固体,83%yield,mp:233-235℃,[α]D 20=-209.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,9H),7.18-7.10(m,3H),7.01-6.89(m,5H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,2H),1.92-1.86(m,2H).MS(MALDI):540[M+H]+.
I-75:
Figure BDA00002801739700273
白色固体,74%yield,mp:235-238℃,[α]D 20=-200.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,9H),7.18-7.10(m,3H),7.01-6.89(m,3H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,8H),1.92-1.86(m,2H).MS(MALDI):568[M+H]+.
I-76:
Figure BDA00002801739700281
MS(MALDI):568[M+H]+.
I-77:
MS(MALDI):624[M+H]+.
I-78:
MS(MALDI):624[M+H]+.
I-79:
Figure BDA00002801739700284
白色固体,65%yield,mp:240-242℃,[α]D 20=-206.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,9H),7.18-7.10(m,3H),7.01-6.89(m,3H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,8H),1.92-1.86(m,2H).1.35(s,18H).MS(MALDI):652[M+H]+.
I-80
Figure BDA00002801739700291
MS(MALDI):652[M+H]+.
I-81:
白色固体,66%yield,mp:240-242℃,[α]D 20=-208.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,14H),7.18-7.10(m,5H),7.01-6.89(m,4H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,8H),1.92-1.86(m,2H).MS(MALDI):692[M+H]+.
I-82:
Figure BDA00002801739700293
MS(MALDI):692[M+H]+.
I-83:
Figure BDA00002801739700294
MS(MALDI):828[M+H]+.
I-84：
Figure BDA00002801739700301
MS(MALDI):828[M+H]+.
I-85:
Figure BDA00002801739700302
MS(MALDI):964[M+H]+.
I-86:
MS(MALDI):964[M+H]+.
I-87:
Figure BDA00002801739700304
MS(MALDI):860[M+H]+.
I-88:
MS(MALDI):860[M+H]+.
I-89：
MS(MALDI):844[M+H]+.
I-90:
Figure BDA00002801739700312
MS(MALDI):844[M+H]+.
I-91:
Figure BDA00002801739700313
白色固体,65%yield,mp:240-242℃,[α]D 20=-206.5(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.35-7.17(m,9H),7.18-7.10(m,3H),7.01-6.89(m,3H),6.81-6.73(m,3H),6.50(d,J=7.8Hz,1H),5.95(d,J=11.4Hz,1H),3.05-2.96(m,2H),2.81-2.71(m,2H),2.21-2.11(m,8H),1.92-1.86(m,2H).MS(MALDI):696[M+H]+.
I-92:
Figure BDA00002801739700314
MS(MALDI):696[M+H]+.
I-93:
Figure BDA00002801739700321
MS(MALDI):792[M+H]+.
I-94:
Figure BDA00002801739700322
MS(MALDI):792[M+H]+.
I-95:
Figure BDA00002801739700323
白色固体,65%yield,mp:204-206℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),2.26(s,18H).MS(MALDI):776[M+H]+.
I-96:
Figure BDA00002801739700324
MS(MALDI):776[M+H]+.
I-97:
白色固体,61%yield,mp:234-236℃,[α]D 20=+200.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,17H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):608[M+H]+.
I-98:
Figure BDA00002801739700332
MS(MALDI):608[M+H]+.
I-99:
Figure BDA00002801739700333
MS(MALDI):608[M+H]+.
I-100:
Figure BDA00002801739700334
MS(MALDI):608[M+H]+.
I-101:
白色固体,65%yield,mp:204-206℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H),3.56(s,3H).MS(MALDI):570[M+H]+.
I-102:
Figure BDA00002801739700342
MS(MALDI):570[M+H]+.
I-103:
MS(MALDI):570[M+H]+.
I-104:
Figure BDA00002801739700344
MS(MALDI):570[M+H]+.
I-105:
Figure BDA00002801739700351
MS(MALDI):600[M+H]+.
I-106:
Figure BDA00002801739700352
MS(MALDI):600[M+H]+.
I-107:
Figure BDA00002801739700353
MS(MALDI):676[M+H]+.
I-108:
MS(MALDI):676[M+H]+.
I-109:
白色固体,68%yield,mp:234-236℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,18H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):590[M+H]+.
I-110:
Figure BDA00002801739700361
MS(MALDI):590[M+H]+.
I-111:
Figure BDA00002801739700362
MS(MALDI):590[M+H]+.
I-112:
Figure BDA00002801739700363
MS(MALDI):590[M+H]+.
I-113:
Figure BDA00002801739700364
白色固体,67%yield,mp:224-226℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,16H),7.03-6.87(m,3H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):537[M+H]+.
I-114:
MS(MALDI):537[M+H]+.
I-115:
Figure BDA00002801739700372
白色固体,65%yield,mp:214-216℃,[α]D 20=+210.7(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.92(d,J=8.7Hz,1H),7.87(d,J=8.1Hz,1H),7.75(d,J=7.8Hz,1H),7.46-7.17(m,14H),7.03-6.87(m,5H),6.75(d,J=8.7Hz,1H),6.10(d,J=9.0Hz,1H).MS(MALDI):554[M+H]+.
I-116:
Figure BDA00002801739700373
MS(MALDI):554[M+H]+.
应用实施例8：
Figure BDA00002801739700374
一般反应操作：氮气保护下，[Ir(cod)Cl]2(1.4mg,0.002mmol)和配体1f(2.3mg,0.004mmol)溶于THF(0.5mL)中，再加入正丙胺(0.3mL)，加热至50℃反应30min，冰浴冷至0℃后，油泵抽干。再依次加入底物(0.1mmol)、溶剂(1mL),K3PO4(21.1mg,0.1mmol)。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/丙酮=3/1)。产物的ee值由HPLC测定。
II-1：
Figure BDA00002801739700381
黄色油状液体,80%yield,96%ee.[层析柱Phenomenex Lux5u Cellulose-2PC-2(0.46cm x25cm),正-己烷exane/2-丙醇2-propanol=98/2,v=0.5mL·min-1,λ=230nm,t(minor)=19.49min,t(major)=16.93min].[α]D 20=-25.9(c1.0,CHCl3).1HNMR(300MHz,CDCl3)δ7.76(s,1H),7.53(d,J=7.2Hz,1H),7.39-7.28(m,5H),7.20(d,J=8.1Hz,1H),7.11-7.00(m,2H),5.93(ddd,J=9.6,9.9,17.7Hz,1H),5.26(d,J=16.5Hz,1H),5.12(d,J=10.2Hz,1H),3.77-3.66(m,3H),3.56(AB,JAB=15.0Hz,1H),3.50(BA,JBA=14.7Hz,1H),2.96(dd,J=5.1,12.0Hz,1H),2.62(dd,J=7.2,11.7Hz,1H).
II-2：
Figure BDA00002801739700382
黄色固体,m.p.=70-72℃,63%yield,88%ee.[层析柱Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=13.41min,t(major)=6.56min].[α]D 20=-17.6(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ8.01(s,1H),7.53(d,J=7.5Hz,1H),7.21(d,J=8.4Hz,1H),7.10(t,J=6.3Hz,1H),7.04(t,J=8.1Hz,1H),5.98-5.86(m,2H),5.32-5.13(m,4H),3.76-3.69(m,1H),3.58(s,2H),3.21-3.16(m,2H),2.93(dd,J=5.1,11.7Hz,1H),2.58(dd,J=6.9,11.4Hz,1H).13C NMR(100MHz,CDCl3)δ140.2,136.1,135.1,131.9,127.0,121.2,119.2,119.1,118.1,115.6,110.7,109.8,60.6,56.9,50.1,38.4;IR(film):vmax(cm-1)=3161,2977,2814,1455,1329,1300,1113,928,736;HRMS(ESI):Exact mass calcd.for C16H18N2[M]:238.1470.Found:238.1470.
II-3：
Figure BDA00002801739700391
黄色固体,m.p.=132-134℃,88%yield,96%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=12.28min,t(major)=8.12min].[α]D 20=-26.1(c=1.0,CHCl3).1H NMR(400MHz,CDCl3)δ7.68(br s,1H),7.38-7.26(m,5H),7.17(dd,J=1.8,9.6Hz,1H),7.11(dd,J=4.4,8.8Hz,1H),6.82(dt,J=1.8,9.6Hz,1H),5.89(ddd,J=8.4,10.0,17.2Hz,1H),5.27(d,J=17.2Hz,1H),5.15(d,J=10.0Hz,1H),3.78-3.65(m,3H),3.56(AB,JAB=14.8Hz,1H),3.53(BA,JBA=14.8Hz,1H),2.96(dd,J=5.2,11.6Hz,1H),2.60(dd,J=7.2,11.6Hz,1H);13C NMR(100MHz,CDCl3)δ156.6(d,J=232.3Hz),139.8,138.1,134.1,132.5,129.0,128.4,127.4(d,J=10.1Hz),127.3,115.7,111.0(d,J=9.6Hz),110.1(d,J=4.5Hz),109.3(d,J=24.1Hz),104.2(d,J=23.8Hz),62.0,57.2,50.1,38.5;19F NMR(386Hz,CDCl3)δ-124.7(m,1F);IR(film):vmax(cm-1)=3412,2922,2851,1634,1588,1452,1311,1153,991,752;ESI-MS(m/z):307(M+1+);HRMS(ESI):Exact mass calcd.for C20H19N2F[M]+:306.1532.Found:306.1537.
II-4：
Figure BDA00002801739700392
黄色固体,80%yield,94%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=10.46min,t(major)=8.25min].[α]D 20=-22.9(c=1.0,CHCl3).1H NMR(400MHz,CDCl3)δ7.74(br s,1H),7.47(s,1H),7.36-7.28(m,5H),7.07(d,J=8.4Hz,1H),7.01(d,J=8.4Hz,1H),5.87(ddd,J=8.8,10.0,17.6Hz,1H),5.26(d,J=16.8Hz,1H),5.14(d,J=10.0Hz,1H),3.75-3.65(m,3H),3.50(AB,JAB=14.8Hz,1H),3.46(BA,JBA=14.8Hz,1H),2.94(dd,J=4.8,11.6Hz,1H),2.58(dd,J=6.8,11.6Hz,1H).
II-5：
Figure BDA00002801739700393
黄色固体,m.p.=116-118℃,74%yield,94%ee.[Phenomenex Lux5u Cellulose-2PC-2(0.46cmx25cm),n-hexane/2-propanol=98/2,v=0.5mL·min-1,λ=230nm,t(minor)=44.71min,t(major)=38.79min].[α]D 20=-16.1(c1.0,CHCl3).1H NMR(400MHz,CDCl3)δ7.71(s,1H),7.62(d,J=1.2Hz,1H),7.37-7.27(m,5H),7.15(dd,J=2.0,8.8Hz,1H),7.04(d,J=8.8Hz,1H),5.88(ddd,J=8.4,10.0,17.2Hz,1H),5.25(d,J=16.8Hz,1H),5.14(d,J=10.0Hz,1H),3.75-3.63(m,3H),3.51(AB,JAB=14.8Hz,1H),3.47(BA,JBA=14.8Hz,1H),2.94(dd,J=5.2,12.0Hz,1H),2.59(dd,J=7.2,11.6Hz,1H);13C NMR(100MHz,CDCl3)δ139.7,138.0,134.6,133.5,129.0,128.7,128.4,127.3,124.0,121.6,115.9,112.5,112.1,109.7,61.9,57.1,49.9,38.4;IR(film):vmax(cm-1)=3384,2919,2759,1458,1344,1290,1099,997,798,698;HRMS(ESI):calcd.for C20H19N2Br[M]+:366.0732.Found:366.0736.
II-6：
Figure BDA00002801739700401
黄色固体,75%yield,96%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=14.53min,t(major)=6.64min].[α]D 20=-24.1(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.63(s,1H),7.38-7.27(m,6H),7.11(d,J=8.1Hz,1H),6.91(d,J=8.1Hz,1H),5.94(ddd,J=8.1,9.6,17.7Hz,1H),5.26(d,J=17.1Hz,1H),5.13(d,J=9.6Hz,1H),3.78-3.66(m,3H),3.58(AB,JAB=15.0Hz,1H),3.51(BA,JBA=14.4Hz,1H),2.93(dd,J=5.1,11.4Hz,1H),2.63(dd,J=7.2,11.7Hz,1H),2.40(s,3H).
II-7：
Figure BDA00002801739700402
黄色固体,80%yield,94%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=15.70min,t(major)=9.79min].[α]D 20=-24.1(c1.0,CHCl3).1H NMR(300MHz,CDCl3)δ7.70(s,1H),7.38-7.27(m,5H),7.09(d,J=8.4Hz,1H),6.99(d,J=2.1Hz,1H),6.73(dd,J=2.4,8.7Hz,1H),5.92(ddd,J=7.8,9.9,17.7Hz,1H),5.26(d,J=17.1Hz,1H),5.13(d,J=10.2Hz,1H),3.80(s,3H),3.72-3.68(m,3H),3.55(AB,JAB=14.7Hz,1H),3.48(BA,JBA=14.7Hz,1H),2.94(dd,J=5.4,11.7Hz,1H),2.61(dd,J=6.9,11.7Hz,1H).
II-7：
Figure BDA00002801739700411
黄色固体,m.p.=155-157℃.93%yield,95%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=8.17min,t(major)=5.69min].[α]D 20=-22.8(c=1.0,CHCl3)1H NMR(400MHz,CDCl3)δ7.70(s,1H),7.42-7.27(m,6H),7.15(s,1H),7.00(dt,J=1.2,8.4Hz,1H),5.89(ddd,J=8.8,10.0,17.2Hz,1H),5.24(d,J=16.8Hz,1H),5.12(d,J=10.0Hz,1H),3.76-3.65(m,3H),3.52(AB,JAB=15.2Hz,1H),3.48(BA,JBA=15.2Hz,1H),2.95(dd,J=4.8,11.6Hz,1H),2.60(dd,J=7.2,11.6Hz,1H);13C NMR(100MHz,CDCl3)δ139.9,138.0,136.4,132.9,129.0,128.4,127.3,127.0,125.6,119.9,119.8,115.7,110.7,110.0,61.9,57.0,49.9,38.4;IR(film):vmax(cm-1)=3159,2977,2815,1450,1328,1171,1061,1018,913,782,734;HRMS(ESI):calcd.for C20H19N2Cl[M]:322.1237.Found:322.1242.
II-8：
Figure BDA00002801739700412
黄色固体,m.p.=92-94℃,72%yield,95%ee.[Daicel Chiralpak IC(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.7mL·min-1,λ=230nm,t(minor)=34.35min,t(major)=12.23min].[α]D 20=-26.4(c=1.0,CHCl3).1H NMR(400MHz,CDCl3)δ7.67(s,1H),7.40-7.24(m,6H),6.72-6.68(m,2H),5.91(ddd,J=8.4,10.0,17.2Hz,1H),5.25(d,J=16.8Hz,1H),5.11(d,J=10.0Hz,1H),3.74(s,3H),3.70-3.64(m,3H),3.50(AB,JAB=14.8Hz,1H),3.45(BA,JBA=14.8Hz,1H),2.92(dd,J=5.2,11.6Hz,1H),2.59(dd,J=7.2,11.6Hz,1H);13C NMR(100MHz,CDCl3)δ156.8,140.3,138.2,136.8,130.8,129.0,128.3,127.2,121.4,119.5,115.3,109.6,108.6,95.0,61.8,57.1,55.6,50.0,38.5;IR(film):vmax(cm-1)=3395,3158,2855,1629,1495,1284,1199,1159,1027,908,801;HRMS(ESI):calcd.for C21H22N2O[M]:318.1732.Found:318.1736.
应用实施例9：
Figure BDA00002801739700421
一般反应操作：氮气保护下，[Ir(cod)Cl]2(1.4mg,0.002mmol)和配体(2.3mg,0.004mmol)溶于THF(0.5mL)中，再加入正丙胺(0.3mL)，加热至50℃反应30min，冰浴冷至0℃后，油泵抽干。再依次加入底物(0.1mmol)、溶剂(1mL),K3PO4(21.1mg,0.1mmol)。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/丙酮=3/1)。产物的ee值由HPLC测定。
III-1：
棕色固体,m.p.=67-69℃,yield80%,98%ee[Daicel Chiralpak OD-H(0.46cmx25cm),n-hexane/2-propanol=100/1,v=0.7mL·min-1,λ=230nm,t(minor)=39.13min,t(major)=41.43min];[α]D 20=-93.1(c=1.0,acetone).1H NMR(300MHz,CDCl3)δ7.85(br s,1H),7.38(d,J=7.5Hz,2H),7.34-7.23(m,3H),6.62(br s,1H),5.94(br s,1H),5.77(ddd,J=17.7,9.3,8.4Hz,1H),5.19(d,J=17.1Hz,1H),5.10(d,J=9.9Hz,1H),3.70(s,2H),3.61(AB,JAB=13.2Hz,1H),3.59-3.54(m,1H),3.40(BA,JBA=12.9Hz,1H),2.96(dd,J=11.1,5.1Hz,1H),2.42(dd,J=10.8,8.7Hz,1H).13C NMR(75MHz,CDCl3)δ138.7,138.6,129.0,128.2,127.0,126.5,116.8,116.6,115.5,105.5,62.1,56.4,51.3,40.0.IR(thin film):νmax(cm-1)=3384,3027,2934,2877,1708,1677,1494,1453,1069,698;HRMS(ESI)calcd forC16H18N2[M]:238.1470.Found:238.1467.
III-2：
Figure BDA00002801739700423
棕色油状液体,57%yield,98%ee[Phenomenex Lux5u Amylose-2 PA-2(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.5mL·min-1,λ=214nm,t(minor)=14.02min,t(major)=15.79min];[α]D 20=-38.9(c=0.5,acetone).1H NMR(300MHz,CDCl3)δ7.96(s,1H),7.31(d,J=7.8Hz,2H),7.13(d,J=8.4Hz,2H),6.21(d,J=2.4Hz,1H),6.02-5.75(m,2H),5.33-5.15(m,4H),3.68-3.58(m,1H),3.65(AB,JAB=13.2Hz,1H),3.37(BA,JBA=12.3Hz,1H),3.20(d,J=6.6Hz,1H),3.00(dd,J=11.1,5.1Hz,1H),2.41(dd,J=11.7,8.7Hz,1H),2.33(s,3H).13C NMR(75MHz,CDCl3)δ138.4,135.6,135.5,131.5,130.2,129.4,127.4,123.5,117.7,117.3,117.0,102.7,60.7,56.3,51.1,40.0,21.1.IR(thin film):νmax(cm-1)=3289,3019,2973,2798,1704,1532,1480,1094,792;HRMS(ESI)calcd for C19H22N2[M]:278.1783.Found:278.1789.
III-3：
Figure BDA00002801739700431
棕色油状液体,91%yield,99%ee[Daicel Chiralcel OJ-H(0.46cmx25cm),n-hexane/2-propanol=80/20,v=0.7mL·min-1,λ=230nm,t(minor)=26.46min,t(major)=32.69min];[α]D 20=-40.1(c=1.0,丙酮acetone).1H NMR(400MHz,CDCl3)δ8.00(s,1H),7.42-7.39(m,4H),7.35-7.25(m,5H),7.18-7.14(m,1H),6.24(d,J=2.4Hz,1H),5.82(ddd,J=18.4,9.6,8.8Hz,1H),5.29-5.14(m,2H),3.72(s,2H),3.64-3.59(m,1H),3.62(AB,JAB=13.6Hz,1H),3.42(BA,JBA=13.6Hz,1H),3.00(dd,J=11.6,5.6Hz,1H),2.46(dd,J=11.2,8.4Hz,1H).13C NMR(100MHz,CDCl3)δ138.7,138.5,132.9,131.4,129.0,128.8,128.3,128.0,127.0,125.8,123.5,117.6,117.0,103.3,62.1,56.4,51.2,40.1.IR(thin film):νmax(cm-1)=3446,3027,2963,2793,1699,1541,1456,1093,799;HRMS(EI)calcd for C22H22N2[M]+:314.1783.Found:314.1781.
III-4：
Figure BDA00002801739700432
红色油状液体,95%yield,96%ee[Phenomenex Lux 5u Celluloxe-2PC-2(0.46cmx25cm),n-hexane/2-propanol=95/5,v=0.5mL·min-1,λ=214nm,t(minor)=21.21min,t(major)=18.88min];[α]D 20=-28.0(c=0.5,acetone).1H NMR(300MHz,CDCl3)δ7.89(s,1H),7.40(d,J=6.9Hz,2H),7.35-7.24(m,5H),6.87(d,J=8.7Hz,2H),6.12(d,J=2.4Hz,1H),5.82(ddd,J=18.6,9.6,9.0Hz,1H),5.26(dd,J=17.1,1.5Hz,1H),5.14(dd,J=9.9,1.5Hz,1H),3.80(s,3H),3.72(s,2H),3.64-3.60(m,1H),3.62(AB,JAB=13.5Hz,1H),3.41(BA,JBA=12.0Hz,1H),2.99(dd,J=11.1,5.4Hz,1H),2.45(dd,J=11.4,8.4Hz,1H).13C NMR(75MHz,CDCl3)δ158.0,138.7,138.6,131.4,129.0,128.2,127.2,127.0,126.0,125.0,117.3,116.8,114.2,102.2,62.1,56.4,55.3,51.2,40.1.IR(thin film):νmax(cm-1)=3275,3031,2955,2799,1699,1541,1457,1249,1029,792,699;HRMS(EI)calcd forC23H24N2O[M]+:344.1889.Found:344.1888.
III-5：
Figure BDA00002801739700441
棕色固体,m.p.=50-53℃,89%yield,98%ee[Phenomenex Lux 5u Celluloxe-2PC-2(0.46cmx25cm),n-hexane/2-propanol=80/20,v=0.5mL·min-1,λ=214nm,t(minor)=36.13min,t(major)=29.04min];[α]D 20=-31.0(c=1.0,acetone).1HNMR(300MHz,CDCl3)δ8.00(s,1H),7.39(d,J=6.9Hz,2H),7.35-7.23(m,3H),6.94(s,1H),6.93(d,J=6.9Hz,1H),6.81(d,J=8.7Hz,1H),6.13(d,J=2.4Hz,1H),5.82(ddd,J=18.0,9.3,8.7Hz,1H),5.23(d,J=16.2Hz,1H),5.12(d,J=9.9Hz,1H),3.87(s,3H),3.85(s,3H),3.71(s,2H),3.63-3.59(m,1H),3.61(AB,JAB=13.5Hz,1H),3.42(BA,JBA=12.6Hz,1H),2.98(dd,J=11.4,5.4Hz,1H),2.46(dd,J=11.1,8.1Hz,1H).13C NMR(75MHz,CDCl3)δ149.1,147.5,138.6,138.5,131.5,128.9,128.2,127.3,126.9,126.4,117.3,116.7,115.9,111.4,107.7,102.4,62.0,56.4,55.8,55.7,51.1.40.0.IR(thin film):νmax(cm-1)=3365,3080,2934,2795,1701,1528,1495,1254,1024,789,699;HRMS(EI)calcd for C24H26N2O2[M]+:374.1994.Found:374.1996.
III-6：
Figure BDA00002801739700451
棕色固体,m.p.=101-103℃,88%yield,99%ee[Daicel Chiralcel OD-H(0.46cmx25cm),n-hexane/2-propanol=80/20,v=0.8mL·min-1,λ=254nm,t(minor)=7.48min,t(major)=6.78min];[α]D 20=-41.0(c=1.0,acetone).1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.39(d,J=6.8Hz,2H),7.36-7.22(m,5H),7.00(t,J=8.8Hz,2H),6.15(d,J=2.0Hz,1H),5.81(ddd,J=18.4,9.6,8.8Hz,1H),5.25(d,J=17.2Hz,1H),5.14(d,J=9.6Hz,1H),3.71(s,2H),3.62-3.59(m,1H),3.61(AB,JAB=13.2Hz,1H),3.40(BA,JBA=13.2Hz,1H),2.99(dd,J=11.2,5.2Hz,1H),2.45(dd,J=11.2,8.8Hz,1H).13C NMR(100MHz,CDCl3)δ161.2(d,J=243.8Hz),138.6,138.5,130.6,130.0,129.3(d,J=3.0Hz),129.0,128.3,128.2,128.0,125.1(d,J=7.6Hz),117.6,117.0,115.6(d,J=21.6Hz),103.2,62.1,56.4,51.1,40.1.19F NMR(282MHz,CDCl3)δ-116.9(m).IR(thin film):νmax(cm-1)=3422,2987,2943,2765,1559,1476,1456,1225,1028,785,664;HRMS(EI)calcd for C19H21N2F[M]+:332.1689.Found:332.1693.
III-7:
Figure BDA00002801739700452
棕色固体,m.p.=115-117℃,88%yield,99%ee[Daicel Chiralcel OD-H(0.46cmx25cm),n-hexane/2-propanol=90/10,v=0.8mL·min-1,λ=254nm,t(minor)=7.68min,t(major)=8.87min];[α]D 20=-31.0(c=1.0,acetone).1H NMR(400MHz,CDCl3)δ7.98(s,1H),7.39(d,J=6.8Hz,2H),7.34-7.24(m,7H),6.21(d,J=2.4Hz,1H),5.81(ddd,J=18.8,10.0,8.8Hz,1H),5.26(d,J=16.4Hz,1H),5.15(d,J=10.4Hz,1H),3.71(s,2H),3.62-3.59(m,1H),3.61(AB,JAB=13.2Hz,1H),3.40(BA,JBA=13.6Hz,1H),2.99(dd,J=11.2,5.6Hz,1H),2.45(dd,J=11.2,8.4Hz,1H).13C NMR(100MHz,CDCl3)δ138.6,138.3,131.4,131.2,130.3,129.0,128.9,128.5,128.3,127.1,124.6,117.8,117.1,103.8,62.1,56.4,51.1,40.1.IR(thin film):νmax(cm-1)=3425,2987,2949,2773,1517,1491,1456,1231,1027,792,695;HRMS(EI)calcd for C22H21N2Cl[M]+:348.1393.Found:348.1396.
III-8：
棕色固体,m.p.=112-113℃,75%yield,98%ee[Daicel Chiralpak AD-H(0.46cmx25cm),n-hexane/2-propanol=80/20,v=0.4mL·min-1,λ=214nm,t(minor)=23.58min,t(major)=18.63min];[α]D 20=-65.4(c=1.0,acetone).1H NMR(300MHz,CDCl3)δ7.96(s,1H),7.41-7.21(m,9H),6.20(d,J=1.8Hz,1H),5.80(ddd,J=18.3,9.6,8.7Hz,1H),5.25(d,J=16.8Hz,1H),5.15(d,J=9.9Hz,1H),3.70(s,2H),3.62-3.57(m,1H),3.59(AB,JAB=13.8Hz,1H),3.38(BA,JBA=12.6Hz,1H),2.97(dd,J=11.4,5.4Hz,1H),2.44(dd,J=11.4,8.4Hz,1H).13C NMR(75MHz,CDCl3)δ138.6,138.3,131.7,130.2,129.0,128.5,128.2,127.0,124.9,119.1,117.8,117.1,103.8,62.0,56.3,51.0,40.0.IR(thin film):νmax(cm-1)=3412,2948,2929,2772,1581,1492,1456,1231,1026,791,694;HRMS(ESI)calcd for C22H21N2Cl[M]:392.0888.Found:392.0878.
III-9：
Figure BDA00002801739700462
棕色固体,m.p.=75-78℃,75%yield,97%ee[Daicel Chiralpak AD-H(0.46cmx25cm),n-hexane/2-propanol=95/5,v=0.5mL·min-1,λ=230nm,t(minor)=15.96min,t(major)=14.29min];[α]D 20=-63.7(c=1.0,acetone).1H NMR(300MHz,CDCl3)δ7.51(s,1H),7.38(d,J=6.9Hz,2H),7.33-7.21(m,3H),5.78(ddd,J=18.9,9.9,9.0Hz,1H),5.64(d,J=2.4Hz,1H),5.19(d,J=16.8Hz,1H),5.08(d,J=9.9Hz,1H),3.68(s,2H),3.57-3.49(m,1H),3.55(AB,JAB=13.8Hz,1H),3.35(BA,JBA=13.2Hz,1H),2.94(dd,J=10.8,5.4Hz,1H),2.55(q,J=7.5Hz,2H),2.41(dd,J=11.4,8.4Hz,1H),1.19(t,J=7.5Hz,3H).13C NMR(75MHz,CDCl3)δ139.0,138.9,133.6,129.0,128.2,126.9,124.8,116.3,115.5,101.6,62.1,56.5,51.3,40.0,20.9,13.7.IR(thin film):νmax(cm-1)=3241,2962,2930,2752,1707,1602,1495,1454,1261,1028,794,698;HRMS(EI)calcd for C18H22N2[M]+:266.1783.Found:266.1787.
III-10：
Figure BDA00002801739700471
棕色固体,m.p.=103-106℃,61%yield,96%ee[Daicel Chiralcel OD-H(0.46cmx25cm),n-hexane/2-propanol=98/2,v=0.5mL·min-1,λ=230nm,t(minor)=18.29min,t(major)=21.12min];[α]D 20=-61.0(c=1.0,acetone).1H NMR(400MHz,CDCl3)δ7.39(d,J=7.2Hz,2H),7.33-7.24(m,4H),5.78(ddd,J=18.8,10.0,8.8Hz,1H),5.19(dd,J=16.8,2.0Hz,1H),5.07(d,J=10.4,2.0Hz,1H),3.72(AB,JAB=13.2Hz,1H),3.68(BA,JBA=13.6Hz,1H),3.52-3.49(m,2H),3.32-3.28(m,1H),2.92(dd,J=12.0,6.0Hz,1H),2.52(t,J=6.0Hz,2H),2.42(dd,J=8.0,8.4Hz,1H),2.33(t,J=6.0Hz,1H),1.79-1.68(m,4H).13C NMR(75MHz,CDCl3)δ139.1,128.9,128.2,126.9,126.2,124.5,116.2,113.8,113.7,62.2,56.5,50.2,40.3,23.4,23.3,22.8,21.2.IR(thin film):νmax(cm-1)=3185,3061,2955,2929,2746,1730,1600,1454,1081,749,698;HRMS(ESI)calcd for C20H24N2[M]:292.1939.Found:292.1928.

Claims (5)

1.一种含有N－芳基的手性膦氮类化合物，其具有如下的结构式：
Figure FDA00002801739600011
Figure FDA00002801739600012
的光学纯化合物；
其中R1,R2,R3,R4任意选自H、F、Cl、Br、I、C1-C6的烷基、C1-C6的全氟烷基、C1-C6的烷氧基或芳基及取代的芳基；
R5、R6、R7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，或Ar1、Ar2通过C、O连接成环；
n任意选自1、2或3；
上述的芳基为苯基、萘基、蒽基或菲基；
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。
2.一种如权利要求1所述N－芳基的手性膦氮类化合物的合成方法，其特征是在有机溶剂中和-78℃至120℃，具有二酚类骨架化合物、芳香二级胺化合物、三氯化磷和碱反应8小时－24小时；所述具有二酚类骨架化合物、芳香二级胺化合物、三氯化磷、碱的摩尔比为1-1.5:1-1.5:1-1.5:3-10；
所述具有二酚类骨架化合物具有如下结构式：
其中R5、R6、R7和n如权利要求1所述；
所述的芳香二级胺化合物具有如下结构式：
Figure FDA00002801739600031
其中R1、R2、R3、R4、Ar1和Ar2如权利要求1所述；
所述的碱任意选自三乙胺、1,8-二氮杂二环[5,4,0]十一碳-7-烯、1,5-二氮杂二环[4,3,0]壬-5-烯、三乙烯二胺、N,O-双(三甲基硅基)乙酰胺、碳酸铯、碳酸钾，膦酸钾、醋酸钾、膦酸钾、氢化钠、正丁基锂、二（三甲基硅基）氨基钠、二（三甲基硅基）氨基锂、二（三甲基硅基）氨基钾、甲醇钠、质子海绵、叔丁醇钾、叔丁醇钠或二异丙基乙基胺。
3.一种如权利要求2所述N－芳基的手性膦氮类化合物的合成方法，其特征是所述有机溶剂是苯、四氯化碳、石油醚、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、二氧六环或乙腈。
4.一种如权利要求2所述N－芳基的手性膦氮类化合物的合成方法，其特征是所得产物经过重结晶、薄层层析、柱层析或减压蒸馏的分离。
5.如权利要求1所述的N－芳基的手性膦氮类化合物化的用途，其特征是作为手性配体，和金属铱生成配合物，在金属铱催化的不对称烯丙基取代反应中作为有效的催化剂。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254251A (zh) * 2013-05-23 2013-08-21 中国科学院上海有机化学研究所 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
CN104610363A (zh) * 2015-01-23 2015-05-13 中山大学 一类亚磷酰胺配体及其制备方法和应用
CN110003105A (zh) * 2019-04-29 2019-07-12 中国科学院上海有机化学研究所 轴手性吡啶化合物、其制备方法及应用
US10565015B2 (en) 2017-09-18 2020-02-18 The Regents Of The University Of Michigan Spiroketal-based C2-symmetric scaffold for asymmetric catalysis
CN113444125A (zh) * 2020-03-26 2021-09-28 西北大学 新型亚磷酰胺配体及其制备方法和在不对称羰基化反应中的应用
CN115246767A (zh) * 2021-04-26 2022-10-28 惠州凯特立斯科技有限公司 一种大位阻螺环二酚及其双亚膦酸酯化合物的合成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0850945A1 (en) * 1996-12-26 1998-07-01 Takasago International Corporation Chiral diphosphine compound, intermediate for preparing the same, transition metal complex having the same diphosphine compound as ligand and asymmetric hydrogenation catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0850945A1 (en) * 1996-12-26 1998-07-01 Takasago International Corporation Chiral diphosphine compound, intermediate for preparing the same, transition metal complex having the same diphosphine compound as ligand and asymmetric hydrogenation catalyst

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AI-GUO HU, ET AL.: "Monodentate Chiral Spiro Phosphoramidites:Efficient Ligands for Rhodium-Catalyzed Enantioselective Hydrogenation of Enamides", 《ANGEW. CHEM. INT. ED》 *
QINGLE ZENG, ET AL.: "H8-MonoPhos and its application in catalytic enantioselective hydrogenation of a-dehydroamino acids", 《TETRAHEDRON》 *
WEN-BO LIU，ET AL.: "Iridium-Catalyzed Allylic Alkylation Reaction with N-Aryl Phosphoramidite Ligands: Scope and Mechanistic Studies", 《J. AM. CHEM. SOC.》 *
WEN-BO LIU，ET AL.: "Iridium-Catalyzed Allylic Alkylation Reaction with N-Aryl Phosphoramidite Ligands: Scope and Mechanistic Studies", 《J. AM. CHEM. SOC.》, vol. 134, 7 February 2012 (2012-02-07) *

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Publication number Priority date Publication date Assignee Title
CN103254251A (zh) * 2013-05-23 2013-08-21 中国科学院上海有机化学研究所 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
CN103254251B (zh) * 2013-05-23 2016-01-13 中国科学院上海有机化学研究所 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
CN104610363A (zh) * 2015-01-23 2015-05-13 中山大学 一类亚磷酰胺配体及其制备方法和应用
US10565015B2 (en) 2017-09-18 2020-02-18 The Regents Of The University Of Michigan Spiroketal-based C2-symmetric scaffold for asymmetric catalysis
CN110003105A (zh) * 2019-04-29 2019-07-12 中国科学院上海有机化学研究所 轴手性吡啶化合物、其制备方法及应用
CN110003105B (zh) * 2019-04-29 2022-08-09 中国科学院上海有机化学研究所 轴手性吡啶化合物、其制备方法及应用
CN113444125A (zh) * 2020-03-26 2021-09-28 西北大学 新型亚磷酰胺配体及其制备方法和在不对称羰基化反应中的应用
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