CN114671816B - 一种轴手性芳基三氮唑类化合物的制备方法 - Google Patents

一种轴手性芳基三氮唑类化合物的制备方法 Download PDF

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CN114671816B
CN114671816B CN202210368253.9A CN202210368253A CN114671816B CN 114671816 B CN114671816 B CN 114671816B CN 202210368253 A CN202210368253 A CN 202210368253A CN 114671816 B CN114671816 B CN 114671816B
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崔孙良
曾林伟
李嘉铭
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Zhejiang University ZJU
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Abstract

本发明公开了一种轴手性芳基三氮唑类化合物的制备方法，其包括如下步骤：1‑炔基‑2‑萘酚或邻炔基苯酚类化合物、有机叠氮类化合物在金属催化剂和指定构型的手性亚磷酰胺配体的协同作用下于溶剂中发生环加成反应。反应完成后，经后处理得到所述的单一构型的芳基三氮唑类化合物；该制备方法利用经典的炔烃与叠氮的Click反应，在温和的条件下构建了手性轴，反应高效简洁快速，收率、区域与立体选择性均非常高，在轴手性构建和Click化学领域均有非常重要意义，对有机合成、药物化学以及化学生物学具有深远的应用潜力。

Description

一种轴手性芳基三氮唑类化合物的制备方法
技术领域
本发明属于有机合成领域，具体涉及一种轴手性芳基三氮唑类化合物的制备方法。
背景技术
轴手性广泛地存在在于天然产物、药物分子、手性催化剂与手性配体中，近二十年来，轴手性研究是有机不对称合成的热点，国内外众多课题组发展了各式各样的方法构建轴手性化合物(Chem.Rev.2021,121,4805-4902；Chem.Rev.2011,111,563-639；J.Am.Chem.Soc.2021,143,14025-14040)。然而，发展精准、可控的轴手性构建方法仍然具有挑战性。
三氮唑结构在化学、生物学、材料学都有非常重要的应用。其最重要的合成方法是依赖于炔烃和有机叠氮的Huisgen环加成反应，反应式如下：
作为最经典的Click反应之一，区域选择性的Huisgen环加成反应引起了化学家的强烈关注，至今，已经发展了包括端炔、内炔烃与叠氮的区域选择性环加成反应构建各种结构的三氮唑(Angew.Chem.Int.Ed.2001,40,2004-2021；Angew.Chem.Int.Ed.2014,53,1877–1880；ACS Catal.2017,7,7529–7534；Org.Lett.2017,19,6200-6203；Org.Lett.2020,22,2220-2224；Adv.Synth.Catal.2019,361,989–99)。然而，利用炔烃和叠氮的立体选择性环加成反应构建手性轴，制备轴手性的芳基三氮唑类化合物则未见报道。
发明内容
本发明提供了一种轴手性芳基三氮唑类化合物的制备方法，该制备方法能够将炔烃和有机叠氮在金属催化剂和手性亚磷酰胺配体的协同作用下，于溶剂中实现区域和立体选择性的环加成反应，得到单一构型的轴手性芳基三氮唑类化合物。
一种轴手性芳基三氮唑类化合物的制备方法，包括如下步骤：1-炔基-2-萘酚或邻炔基苯酚类化合物、有机叠氮、金属催化剂和S构型或R构型的手性亚磷酰胺配体于溶剂中发生环加成反应，分别得到S构型和R构型的芳基三氮唑类化合物。
述的1-炔基2-萘酚类化合物的结构如式(Ⅶ)所示：
所述的邻炔基苯酚类化合物的结构如式(Ⅷ)所示：
所述的1-炔基二萘胺类化合物的结构如式(Ⅸ)所示：
所述的叠氮化合物结构如式(Ⅹ)所示：
R6-N3(X)；
所述的S构型的轴手性芳基三氮唑的结构如式(Ⅰ)、(Ⅱ)或(Ⅲ)所示：
所述的R构型的轴手性芳基三氮唑的结构如式(IV)、(Ⅴ)或(Ⅵ)所示
式(Ⅰ)～式(Ⅹ)中，R1、R4为未取代或者带各种取代基的苯基、芳杂环、烯基或烷基；
R2、R3独立地选自氢、烷基、苯基、炔基、卤素、醛基、氰基；
R5为未取代或者带各种取代基的烷基、烷氧基、卤素、烯基、保护的醛基；
R6为未取代或者带各种取代基的苯基、芳杂环、未取代或带各种取代基的烷基；
式(Ⅰ)中，X为碳原子或氮原子；
式(IV)中，X为碳原子或氮原子；
式(Ⅶ)中，X为碳原子或氮原子；
式(Ⅱ)中，环状结构为六元碳环或哌啶环；
式(Ⅴ)中，环状结构为六元碳环或哌啶环；
式(Ⅷ)中，环状结构为六元碳环或哌啶环。
本发明中，将1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物与有机叠氮类化合物在金属催化剂和手性亚磷酰胺配体的协同作用下，于溶剂中进行环加成反应得到轴手性芳基三氮唑类化合物，利用不同构型的手性配体，可以选择性得到相应单一构型的轴手性芳基三氮唑类化合物。本方法反应条件温和，效率高、区域和立体选择性优。将Click反应与轴手性构建相结合，利用炔烃与叠氮的环加成反应用于高效合成轴手性的芳基三氮唑类化合物。
上述R1、R2、R3、R4、R5、R6中，所涉及到的烷基优选为C1～C10烷基，进一步优选为C1～C6烷基，更进一步优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基或者叔丁基。
上述R1、R2、R3、R4、R5、R6中，所涉及到的烷氧基优选为C1～C10烷氧基，进一步优选为C1～C6烷氧基，更进一步优选为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或者叔丁氧基。
上述R1、R2、R3、R4、R5、R6中，所涉及到的炔基进一步优选为C2～C10炔基，进一步优选为C2～C6炔基，更进一步优选为C2～C4炔基。上述R1、R2、R3、R4、R5、R6中，所涉及到的烯基进一步优选为C2～C10烯基，进一步优选为C2～C6烯基，更进一步优选为C2～C4烯基。
上述R1、R2、R3、R4、R5、R6中，所涉及到的芳杂环包括2-噻吩基、2-吡啶基或5-吲哚基。
所述的1-炔基-2-萘酚、邻炔基苯酚以及1-炔基-2-萘胺类化合物可以通过现有的合成方法制备，具体可参见文献(J.Am.Chem.Soc.2014,136,4740-4745；Nat.Cat.2019,2,504-513；Org.Lett.2011,13,1250-1253；Org.Chem.Front.2019,6,451-455)。
所述的有机叠氮类化合物可通过现有的合成方法制备，具体可参考文献(J.Am.Chem.Soc.2016,138,8348-8351；Eur.J.Org.Chem.1998,1998,1219-1226；Angew.Chem.In.Ed.2017,56,4320-4323)。
作为优选，所述的1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物、有机叠氮类化合物的摩尔比为1:1.1～1.3，进一步优选为1:1.2，叠氮的适当过量可保证反应比较彻底。
作为优选，所述的金属催化剂为1,5-环辛二烯氯化铱(I)二聚体[Ir(cod)2Cl]2、氯二(环辛烯)铱(I)二聚体[Ir(coe)2Cl]2、氯四乙烯铱(I)二聚体[Ir(η2-ethylene)2Cl]2、甲氧基(1,5-环辛二烯)铱(I)二聚体[Ir(cod)OMe]2、1,5-环辛二烯氯化铑(I)二聚体[Rh(cod)Cl]2、羟基(1,5-环辛二烯)铑(I)二聚体[Rh(cod)(OH)]2中的一种。作为进一步的优选，金属催化剂为[Rh(cod)(OH)]2。
作为优选，所述手性配体为市面上所售的手性亚磷酰胺配体。作为进一步的优选，配体为(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(CAS号:942939-38-0)，以及其对映体(R)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂/>(CAS号:1265884-98-7)，两种构型的配体可分别得到对应的单一构型轴手性芳基三氮唑类化合物。
作为优选，手性配体与金属催化剂的摩尔比应≧2:1，保证催化剂与配体结合完全。作为进一步的优选，手性配体与金属催化剂的摩尔比为2:1，过多加入配体会明显减缓反应速率。
作为优选，所述的溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、乙酸乙酯、乙醚、1,4-二氧六环、甲醇、乙醇、四氢呋喃、甲苯、水、PBS缓冲液的一种或混合溶剂。作为进一步的优选，反应溶剂为二氯甲烷。
作为优选，所述的反应温度为-20～25℃。作为进一步的优选，反应温度为25℃，反应温度降低对立体选择性未有影响，但会显著降低反应速率与原料转化率。
本发明中，反应的时间可以通过薄层层析(TLC)进行监测，一般进行2-24小时后，反应可进行彻底。
本发明提供了一条利用炔烃和叠氮的不对称Click环加成反应构建轴手性的芳基三氮唑类化合物，在有机合成、药物化学、化学生物学领域具有很大的应用潜力与价值，该合成方法未见报道。
附图说明
图1为实施例1所制得的S构型产物的1H NMR谱图。
图2为实施例1所制得的S构型产物的13C NMR谱图；
图3为实施例1所制得的R构型产物的1H NMR谱图；
图4为实施例1所制得的R构型产物的13C NMR谱图；
图5为实施例1所制得的产物的消旋体HPLC图；
图6为实施例1所制得的S构型产物的HPLC图；
图7为实施例1所制得的R构型产物的HPLC图；
图8为实施例1所制得的S构型产物单晶结构图；
图9为实施例1所制得的R构型产物单晶结构图。
图10为实施例45所制得的S构型产物的1H NMR谱图。
图11为实施例45所制得的S构型产物的13C NMR谱图；
图12为实施例45所制得的R构型产物的1H NMR谱图；
图13为实施例45所制得的R构型产物的13C NMR谱图；
图14为实施例45所制得的产物的消旋体HPLC图；
图15为实施例45所制得的S构型产物的HPLC图；
图16为实施例45所制得的R构型产物的HPLC图；
具体实施方式
实施例1
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率95％，ee值94％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率96％，ee值-94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点213–214℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝8.75min,t(minor)＝7.42min.]1H NMR(400MHz,CDCl3)δ8.22(s,1H),7.93(d,J＝9.2Hz,1H),7.76(d,J＝8.0Hz,1H),7.37(d,J＝9.2Hz,1H),7.34–7.29(m,2H),7.25–7.20(m,1H),7.07–6.88(m,7H),6.84–6.79(m,2H),6.70(d,J＝8.4Hz,1H),5.29(d,J＝14.4Hz,1H),5.19(d,J＝14.4Hz,1H).13C NMR(100MHz,CDCl3)δ154.3,146.7,134.0,132.8,132.6,129.8,128.7,128.53,128.45,128.4,128.2,127.8,127.5,127.3,125.8,123.9,123.4,119.1,105.9,53.1.HRMS(ESI-TOF)C25H20N3O(M+H)+:378.1606；Found:378.1606.
R型产物：白色固体，熔点216–217℃；-94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.44min,t(minor)＝8.95min.].1H NMR(400MHz,CDCl3)δ8.15(s,1H),7.93(d,J＝9.2Hz,1H),7.76(d,J＝8.0Hz,1H),7.36(d,J＝9.2Hz,1H),7.34–7.28(m,2H),7.24–7.20(m,1H),7.08–6.88(m,7H),6.84–6.79(m,2H),6.71(d,J＝8.4Hz,1H),5.28(d,J＝14.4Hz,1H),5.19(d,J＝14.4Hz,1H).13C NMR(100MHz,CDCl3)δ154.3,146.7,134.0,132.8,132.6,129.8,128.7,128.52,128.46,128.4,128.2,127.9,127.6,127.3,125.8,123.9,123.4,119.1,105.9,53.1.HRMS(ESI-TOF)C25H20N3O(M+H)+:378.1606；Found:378.1605.
核磁谱图、HPLC图及单晶结构见图1-图9。
实施例2
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苯基叠氮(14mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值94％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苯基叠氮(14mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-90％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点290–291℃；94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.92min,t(minor)＝4.36min.].1H NMR(400MHz,DMSO-d6)δ10.44(s,1H),7.94(d,J＝9.2Hz,1H),7.83(d,J＝8.0Hz,1H),7.52–7.45(m,2H),7.41–7.18(m,11H),7.03(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,144.8,136.4,133.0,132.2,130.9,129.23,129.19,128.6,128.5,127.8,127.7,127.6,125.5,124.0,123.3,122.5,118.1,106.0.HRMS(ESI-TOF)Calcd for C24H18N3O(M+H)+:364.1450；Found:364.1450.
R型产物：白色固体，熔点293–294℃；-90％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.28min,t(minor)＝5.87min.]1H NMR(400MHz,DMSO-d6)δ10.45(s,1H),7.94(d,J＝9.2Hz,1H),7.83(d,J＝8.0Hz,1H),7.52–7.46(m,2H),7.41–7.18(m,11H),7.03(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,144.8,136.4,133.0,132.2,130.9,129.22,129.17,128.6,128.5,127.9,127.7,127.6,125.5,124.0,123.3,122.5,118.1,106.0.HRMS(ESI-TOF)Calcd for C24H18N3O(M+H)+:364.1450；Found:364.1451.
实施例3
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-氟苯基叠氮(16.5mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物34.7mg，收率91％，ee值91％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-氟苯基叠氮(16.5mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物34.3mg，收率90％，ee值-92％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点277–278℃；91％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝11.72min,t(minor)＝7.55min.][α]D,25＝+13.5(c＝0.4,DMSO).1H NMR(400MHz,DMSO-d6)δ10.38(s,1H),7.89(d,J＝9.2Hz,1H),7.80(d,J＝8.0Hz,1H),7.54–7.47(m,2H),7.46–7.38(m,2H),7.34–7.15(m,8H),7.10(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ156.2(d,JF-C＝252.6Hz),154.7,144.3,132.8,132.2,132.1,130.8(d,JF-C＝6.8Hz),128.7,128.4,128.3,127.9,127.5,125.5,124.7(d,JF-C＝3.5Hz),123.9(d,JF-C＝12.2Hz),123.3,122.5,118.0,116.7(d,JF-C＝19.2Hz),105.1.19F NMR(565MHz,DMSO-d6)δ-121.79.HRMS(ESI-TOF)Calcd for C24H17FN3O(M+H)+:382.1356；Found:382.1358.
R型产物：白色固体，熔点279–280℃；-92％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.65min,t(minor)＝12.36min.][α]D,25＝-12.9(c＝0.4,DMSO).1H NMR(400MHz,DMSO-d6)δ10.41(s,1H),7.89(d,J＝9.2Hz,1H),7.80(d,J＝8.0Hz,1H),7.54–7.46(m,2H),7.46–7.36(m,2H),7.34–7.15(m,8H),7.09(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ156.2(d,JF-C＝252.6Hz),154.7,144.3,132.8,132.2,132.1,130.8(d,JF-C＝6.8Hz),128.7,128.4,128.3,127.9,127.4,125.5,124.7(d,JF-C＝3.5Hz),123.9(d,JF-C＝12.2Hz),123.3,122.5,118.0,116.7(d,JF-C＝19.2Hz),105.1.19F NMR(565MHz,DMSO-d6)δ-121.79.HRMS(ESI-TOF)Calcd for C24H17FN3O(M+H)+:382.1356；Found:382.1358.实施例4
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应6小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率96％，ee值91％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应6小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-91％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点139–141℃；91％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.79min,t(minor)＝4.17min.].1H NMR(400MHz,DMSO-d6)δ10.60(s,1H),8.03(d,J＝7.2Hz,1H),7.92(d,J＝8.4Hz,1H),7.83(d,J＝8.0Hz,1H),7.66–7.56(m,2H),7.55–7.49(m,2H),7.37–7.20(m,7H),7.15(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,144.7,137.3,134.3,134.0,132.6,132.5,130.8,130.4,130.2,128.8,128.6,128.1,127.8,127.6,126.5,125.5,123.5,122.3,118.0,115.6,109.9,104.7.HRMS(ESI-TOF)Calcd for C25H17N4O(M+H)+:389.1402；Found:389.1398.
R型产物：白色固体，熔点139–141℃；91％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.37min,t(minor)＝5.07min.].1H NMR(400MHz,DMSO-d6)δ10.55(s,1H),8.03(d,J＝7.2Hz,1H),7.92(d,J＝8.4Hz,1H),7.83(d,J＝8.0Hz,1H),7.66–7.56(m,2H),7.55–7.49(m,2H),7.37–7.20(m,7H),7.15(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,144.7,137.3,134.3,134.0,132.6,132.5,130.8,130.4,130.2,128.8,128.6,128.1,127.8,127.6,126.5,125.5,123.5,122.3,118.0,115.6,109.9,104.7.HRMS(ESI-TOF)Calcd for C25H17N4O(M+H)+:389.1402；Found:389.1398.
实施例5
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率94％，ee值92％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-93％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点217–219℃；92％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝23.24min,t(minor)＝11.10min.].1H NMR(400MHz,DMSO-d6)δ10.60(s,1H),7.98(d,J＝8.8Hz,1H),7.92(s,1H),7.85(d,J＝7.6Hz,2H),7.65(d,J＝8.8Hz,1H),7.60–7.54(m,1H),7.52–7.47(m,2H),7.36–7.19(m,6H),7.07(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,145.0,136.8,133.2,132.8,132.6,130.8,130.6,129.4,128.8,128.7,128.6,128.04,127.97,127.68,127.65,125.6,123.5,122.5,118.1,117.5,112.2,105.3.HRMS(ESI-TOF)Calcd for C25H17N4O(M+H)+:389.1402；Found:389.1402.R型产物：白色固体，熔点216–219℃；-93％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝11.62min,t(minor)＝23.08min.].1H NMR(400MHz,DMSO-d6)δ10.63(s,1H),7.98(d,J＝8.8Hz,1H),7.92(s,1H),7.85(d,J＝7.6Hz,2H),7.65(d,J＝8.8Hz,1H),7.60–7.54(m,1H),7.52–7.47(m,2H),7.36–7.19(m,6H),7.07(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,145.0,136.8,133.2,132.8,132.6,130.8,130.6,129.4,128.8,128.7,128.6,128.03,127.96,127.69,127.66,125.6,123.5,122.4,118.1,117.5,112.2,105.3.HRMS(ESI-TOF)Calcd forC25H17N4O(M+H)+:389.1402；Found:389.1402.
实施例6
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-三氟甲基苯基叠氮(22.5mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值91％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-三氟甲基苯基叠氮(22.5mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率94％，ee值-92％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点196–198℃；91％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.17min,t(minor)＝5.89min.].1H NMR(400MHz,DMSO-d6)δ10.60(s,1H),7.97(d,J＝8.8Hz,1H),7.85(d,J＝8.0Hz,1H),7.77–7.68(m,3H),7.66–7.59(m,1H),7.55–7.48(m,2H),7.35–7.20(m,6H),7.08(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ155.0,145.1,136.7,132.8,132.5,130.8,130.6,129.8(q,JF-C＝32.5Hz),129.3,128.7,128.6,128.03,127.99,127.9,127.7,126.0(q,JF-C＝2.9Hz),125.6,123.5,123.25(q,JF-C＝272.6Hz),122.4,120.5(q,JF-C＝3.8Hz),118.0,105.4.19F NMR(565MHz,DMSO-d6)δ-61.64.HRMS(ESI-TOF)Calcd for C25H17F3N3O(M+H)+:432.1324；Found:432.1324.
R型产物：白色固体，熔点197–199℃；-93％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.43min,t(minor)＝6.80min.].1H NMR(400MHz,DMSO-d6)δ10.60(s,1H),7.97(d,J＝8.8Hz,1H),7.85(d,J＝8.0Hz,1H),7.77–7.68(m,3H),7.66–7.59(m,1H),7.55–7.48(m,2H),7.35–7.20(m,6H),7.08(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ155.0,145.1,136.7,132.8,132.5,130.8,130.6,129.8(q,JF-C＝32.5Hz),129.3,128.7,128.6,128.03,127.99,127.9,127.7,126.0(q,JF-C＝2.9Hz),125.6,123.5,123.25(q,JF-C＝272.6Hz),122.4,120.5(q,JF-C＝3.8Hz),118.0,105.4.19F NMR(565MHz,DMSO-d6)δ-61.64.HRMS(ESI-TOF)Calcd for C25H17F3N3O(M+H)+:432.1324；Found:432.1324.
实施例7
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率95％，ee值95％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-氰基苯基叠氮(17.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-90％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点267–268℃；95％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝0.8mL·min–1,λ＝254nm),t(major)＝19.30min,t(minor)＝16.18min.].1H NMR(400MHz,DMSO-d6)δ10.60(s,1H),7.98(d,J＝8.8Hz,1H),7.92(s,1H),7.85(d,J＝7.6Hz,2H),7.65(d,J＝8.8Hz,1H),7.60–7.54(m,1H),7.52–7.47(m,2H),7.36–7.19(m,6H),7.07(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,145.0,136.8,133.2,132.8,132.6,130.8,130.6,129.4,128.8,128.7,128.6,128.04,127.97,127.68,127.65,125.6,123.5,122.5,118.1,117.5,112.2,105.3.HRMS(ESI-TOF)Calcd for C25H17N4O(M+H)+:389.1402；Found:389.1402.R型产物：白色固体，熔点265–268℃；90％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝0.8mL·min–1,λ＝254nm),t(major)＝16.31min,t(minor)＝19.44min.].1HNMR(400MHz,DMSO-d6)δ10.64(s,1H),7.98(d,J＝8.8Hz,1H),7.92(s,1H),7.85(d,J＝7.6Hz,2H),7.65(d,J＝8.8Hz,1H),7.60–7.54(m,1H),7.52–7.47(m,2H),7.36–7.19(m,6H),7.07(d,J＝8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,145.0,136.8,133.2,132.8,132.6,130.8,130.6,129.4,128.8,128.7,128.6,128.04,127.97,127.68,127.65,125.6,123.5,122.5,118.1,117.5,112.2,105.3.HRMS(ESI-TOF)Calcd for C25H17N4O(M+H)+:389.1402；Found:389.1402.
实施例8
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-羟基苯基叠氮(16.2mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率95％，ee值93％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-羟基苯基叠氮(16.2mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-90％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点184–185℃；93％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.69min,t(minor)＝4.68min.].1H NMR(400MHz,DMSO-d6)δ10.35(br,1H),9.86(br,1H),7.92(d,J＝9.2Hz,1H),7.82(d,J＝7.6Hz,1H),7.50–7.45(m,2H),7.33–7.15(m,8H),7.00(d,J＝8.0Hz,1H),6.72–6.60(m,2H).13C NMR(100MHz,DMSO-d6)δ158.0,154.9,144.4,133.1,131.9,131.2,129.3,128.6,128.4,127.9,127.62,127.57,125.6,125.4,123.2,122.5,118.1,115.4,106.3.HRMS(ESI-TOF)Calcd for C24H18N3O2(M+H)+:380.1399；Found:380.1399.
R型产物：白色固体，熔点183–184℃；-90％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.49min,t(minor)＝7.45min.].1H NMR(400MHz,DMSO-d6)δ10.35(br,1H),9.86(br,1H),7.92(d,J＝9.2Hz,1H),7.82(d,J＝7.6Hz,1H),7.50–7.45(m,2H),7.33–7.15(m,8H),7.00(d,J＝8.0Hz,1H),6.72–6.60(m,2H).13C NMR(100MHz,DMSO-d6)δ158.0,154.9,144.4,133.1,131.9,131.2,129.3,128.6,128.4,127.9,127.62,127.57,125.6,125.4,123.2,122.5,118.1,115.4,106.3.HRMS(ESI-TOF)Calcd for C24H18N3O2(M+H)+:380.1399；Found:380.1399.
实施例9
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-氨基苯基叠氮(16.1mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值94％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-氨基苯基叠氮(16.1mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值-93％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点255–256℃；94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.69min,t(minor)＝5.04min.].1H NMR(400MHz,DMSO-d6)δ10.34(s,1H),7.91(d,J＝8.8Hz,1H),7.82(d,J＝7.6Hz,1H),7.53–7.43(m,2H),7.34–7.14(m,6H),7.04–6.96(m,3H),6.39(d,J＝8.8Hz,2H),5.35(s,2H).13C NMR(100MHz,DMSO-d6)δ154.8,149.5,144.2,133.2,131.8,131.4,129.2,128.6,128.4,127.6,127.54,127.51,125.4,125.2,124.8,123.2,122.63,118.1,113.1,106.7.HRMS(ESI-TOF)Calcd for C24H19N4O(M+H)+:379.1559；Found:379.1558.
R型产物：白色固体，熔点256–258℃；94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.86min,t(minor)＝6.39min.].1H NMR(400MHz,DMSO-d6)δ10.34(s,1H),7.91(d,J＝8.8Hz,1H),7.82(d,J＝7.6Hz,1H),7.53–7.43(m,2H),7.34–7.14(m,6H),7.04–6.96(m,3H),6.39(d,J＝8.8Hz,2H),5.35(s,2H).13C NMR(100MHz,DMSO-d6)δ154.8,149.5,144.2,133.2,131.8,131.4,129.2,128.6,128.4,127.6,127.54,127.51,125.4,125.2,124.8,123.2,122.63,118.1,113.1,106.7.HRMS(ESI-TOF)Calcd for C24H19N4O(M+H)+:379.1559；Found:379.1558.
实施例10
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-乙酰基苯基叠氮(19.3mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率92％，ee值89％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-乙酰基苯基叠氮(19.3mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值-89％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点224–225℃；89％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.38min,t(minor)＝5.73min.].1H NMR(400MHz,DMSO-d6)δ10.46(s,1H),7.96–7.75(m,4H),7.50–7.38(m,4H),7.28–7.12(m,6H),6.99(d,J＝8.0Hz,1H),2.43(s,3H).13C NMR(100MHz,DMSO-d6)δ197.0,154.9,145.2,139.7,136.9,132.9,132.4,130.7,129.3,129.2,128.7,128.6,128.0,127.9,127.7,125.6,123.8,123.5,122.4,118.2,105.6,26.8.HRMS(ESI-TOF)Calcd for C26H20N3O2(M+H)+:406.1556；Found:406.1556.
R型产物：白色固体，熔点221–222℃；89％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.64min,t(minor)＝6.73min.].1H NMR(400MHz,DMSO-d6)δ10.46(s,1H),7.96–7.75(m,4H),7.50–7.38(m,4H),7.28–7.12(m,6H),6.99(d,J＝8.0Hz,1H),2.43(s,3H).13C NMR(100MHz,DMSO-d6)δ197.0,154.9,145.2,139.7,136.9,132.9,132.4,130.7,129.3,129.2,128.7,128.6,128.0,127.9,127.7,125.6,123.8,123.5,122.4,118.2,105.6,26.8.HRMS(ESI-TOF)Calcd for C26H20N3O2(M+H)+:406.1556；Found:406.1556.
实施例11
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-叠氮苯甲酸甲酯(21.3mg,0.12mmol)，反应于室温下敞口反应8小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率94％，ee值89％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-叠氮苯甲酸甲酯(21.3mg,0.12mmol)，反应于室温下敞口反应8小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-82％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点224–225℃；89％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.78min,t(minor)＝4.33min.].1H NMR(400MHz,DMSO-d6)δ10.46(s,1H),7.96–7.75(m,4H),7.50–7.38(m,4H),7.28–7.12(m,6H),6.99(d,J＝8.0Hz,1H),2.43(s,3H).13C NMR(100MHz,DMSO-d6)δ197.0,154.9,145.2,139.7,136.9,132.9,132.4,130.7,129.3,129.2,128.7,128.6,128.0,127.9,127.7,125.6,123.8,123.5,122.4,118.2,105.6,26.8.HRMS(ESI-TOF)Calcd for C26H20N3O2(M+H)+:406.1556；Found:406.1556.
R型产物：白色固体，熔点221–223℃；82％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.02min,t(minor)＝7.02min.].1H NMR(400MHz,DMSO-d6)δ10.46(s,1H),7.96–7.75(m,4H),7.50–7.38(m,4H),7.28–7.12(m,6H),6.99(d,J＝8.0Hz,1H),2.43(s,3H).13C NMR(100MHz,DMSO-d6)δ197.0,154.9,145.2,139.7,136.9,132.9,132.4,130.7,129.3,129.2,128.7,128.6,128.0,127.9,127.7,125.6,123.8,123.5,122.4,118.2,105.6,26.8.HRMS(ESI-TOF)Calcd for C26H20N3O2(M+H)+:406.1556；Found:406.1556.
实施例12
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3,5-二氟苯基叠氮(18.6mg，0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值92％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点249–251℃；92％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝12.18min,t(minor)＝5.89min.]1H NMR(400MHz,DMSO-d6)δ10.63(s,1H),8.00(d,J＝9.2Hz,1H),7.87(d,J＝7.6Hz,1H),7.53–7.45(m,2H),7.38–7.13(m,9H),7.06(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ161.9(dd,JF-C,1＝247.6Hz,JF-C,2＝14.5Hz),155.0,145.2,138.1(t,JF-C＝13.2Hz),132.8,132.7,130.5,129.3,128.8,128.6,128.1,128.0,127.7,125.6,123.6,122.4,118.1,108.0(dd,JF-C,1＝21.2Hz,JF-C,2＝8.5Hz),105.3,105.1(t,JF-C＝25.8Hz).19F NMR(565MHz,DMSO-d6)δ-107.68.HRMS(ESI-TOF)Calcd forC24H16F2N3O(M+H)+:400.1261；Found:400.1261.
实施例13
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-萘基叠氮(20.3mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值91％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点219–221℃；91％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.25min,t(minor)＝5.13min.][α]D,25＝+1.8(c＝0.4,DMSO).1H NMR(400MHz,DMSO)δ10.49(s,1H),8.04(d,J＝1.6Hz,1H),7.93(d,J＝9.2Hz,1H),7.89–7.78(m,4H),7.57–7.49(m,4H),7.42(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.34–7.19(m,6H),7.10(d,J＝8.0Hz,1H).13CNMR(100MHz,DMSO)δ154.9,144.9,133.8,133.0,132.4,132.3,132.2,130.9,129.4,129.0,128.7,128.5,128.1,127.82,127.75,127.7,127.6,127.27,127.25,125.5,123.3,122.8,122.5,121.7,118.1,106.1.HRMS(ESI-TOF)Calcd for C28H20N3O(M+H)+:414.1606；Found:414.1606.
实施例14
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-吡啶叠氮(14.4mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值94％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-吡啶叠氮(14.4mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值-93％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点139–141℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝11.89min,t(minor)＝8.54min.].1H NMR(400MHz,DMSO-d6)δ10.54(s,1H),8.59–8.52(m,2H),7.96(d,J＝8.8Hz,1H),7.87–7.79(m,2H),7.54–7.47(m,2H),7.44(dd,J1＝8.0Hz,J2＝4.8Hz,1H),7.36–7.20(m,6H),7.09(d,J＝8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ154.9,150.3,145.0,144.5,133.0,132.8,132.5,131.8,130.6,129.6,128.7,128.6,128.01,127.96,127.6,125.5,124.2,123.5,122.5,118.1,105.3.HRMS(ESI-TOF)Calcd forC23H17N4O(M+H)+:365.1402；Found:365.1403.
R型产物：白色固体，熔点139–141℃；-93％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝8.89min,t(minor)＝11.54min.][α]D,25＝+40.9(c＝0.4,DMSO).1H NMR(400MHz,DMSO-d6)δ10.54(s,1H),8.59–8.52(m,2H),7.96(d,J＝8.8Hz,1H),7.87–7.79(m,2H),7.54–7.47(m,2H),7.44(dd,J1＝8.0Hz,J2＝4.8Hz,1H),7.36–7.20(m,6H),7.09(d,J＝8.0Hz,1H).13CNMR(100MHz,DMSO-d6)δ154.9,150.3,145.0,144.5,133.0,132.8,132.5,131.8,130.6,129.6,128.7,128.6,128.01,127.96,127.6,125.5,124.2,123.5,122.5,118.1,105.3.HRMS(ESI-TOF)Calcd for C23H17N4O(M+H)+:365.1402；Found:365.1403.
实施例15
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入5-吲哚基叠氮(19.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率95％，ee值96％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入5-吲哚基叠氮(19.0mg，0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值-93％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点230–232℃；96％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝8.83min,t(minor)＝6.48min.].1H NMR(400MHz,DMSO-d6)δ11.31(s,1H),10.42(br,1H),7.88(d,J＝8.8Hz,1H),7.77(d,J＝8.0Hz,1H),7.61(d,J＝1.6Hz,1H),7.52–7.48(m,2H),7.40–7.36(m,1H),7.32–7.18(m,7H),7.08(dd,J1＝8.8Hz,J2＝1.6Hz,1H),7.05(d,J＝8.0Hz,1H),6.38(s,1H).13C NMR(100MHz,DMSO-d6)δ155.0,144.3,135.5,133.2,131.8,131.3,129.6,128.6,128.5,128.4,127.59,127.55,127.5,127.4,127.0,125.4,123.2,122.6,118.1,117.6,116.3,111.5,106.7,101.7.HRMS(ESI-TOF)Calcd for C26H19N4O(M+H)+:403.1559；Found:403.1560.
R型产物：白色固体，熔点230–232℃；-93％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.13min,t(minor)＝8.59min.].1H NMR(400MHz,DMSO-d6)δ11.31(s,1H),10.42(br,1H),7.88(d,J＝8.8Hz,1H),7.77(d,J＝8.0Hz,1H),7.61(d,J＝1.6Hz,1H),7.52–7.48(m,2H),7.40–7.36(m,1H),7.32–7.18(m,7H),7.08(dd,J1＝8.8Hz,J2＝1.6Hz,1H),7.05(d,J＝8.0Hz,1H),6.38(s,1H).13C NMR(100MHz,DMSO-d6)δ155.0,144.3,135.5,133.2,131.8,131.3,129.6,128.6,128.5,128.4,127.59,127.55,127.5,127.4,127.0,125.4,123.2,122.6,118.1,117.6,116.3,111.5,106.7,101.7.HRMS(ESI-TOF)Calcd for C26H19N4O(M+H)+:403.1559；Found:403.1560.
实施例16
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-呋喃基甲基叠氮(14.8mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值97％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-呋喃基甲基叠氮(14.8mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点200–202℃；97％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.70min,t(minor)＝4.29min.]1H NMR(400MHz,CDCl3)δ8.89(s,1H),7.86(d,J＝8.8Hz,1H),7.70(d,J＝8.0Hz,1H),7.34(d,J＝8.8Hz,1H),7.21–7.14(m,3H),7.10–7.04(m,1H),7.02(dd,J1＝1.6Hz,J2＝0.4Hz,1H),6.85–6.71(m,4H),5.94(dd,J1＝3.2Hz,J2＝2.0Hz,1H),5.71(d,J＝3.2Hz,1H),5.34(d,J＝15.6Hz,1H),5.15(d,J＝15.6Hz,1H).13C NMR(100MHz,CDCl3)δ154.8,147.0,146.5,143.1,132.9,132.6,129.5,128.7,128.4,128.2,127.8,127.6,127.5,125.8,123.8,123.4,119.4,110.5,110.1,105.4,45.6.HRMS(ESI-TOF)Calcd for C23H18N3O2(M+H)+:368.1399；Found:368.1397.
R型产物：白色固体，熔点200–202℃；-95％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.27min,t(minor)＝4.68min.].1H NMR(400MHz,CDCl3)δ8.89(s,1H),7.86(d,J＝8.8Hz,1H),7.70(d,J＝8.0Hz,1H),7.34(d,J＝8.8Hz,1H),7.21–7.14(m,3H),7.10–7.04(m,1H),7.02(dd,J1＝1.6Hz,J2＝0.4Hz,1H),6.85–6.71(m,4H),5.94(dd,J1＝3.2Hz,J2＝2.0Hz,1H),5.71(d,J＝3.2Hz,1H),5.34(d,J＝15.6Hz,1H),5.15(d,J＝15.6Hz,1H).13C NMR(100MHz,CDCl3)δ154.8,147.0,146.5,143.1,132.9,132.6,129.5,128.7,128.4,128.2,127.8,127.6,127.5,125.8,123.8,123.4,119.4,110.5,110.1,105.4,45.6.HRMS(ESI-TOF)Calcd for C23H18N3O2(M+H)+:368.1399；Found:368.1397.
实施例17
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-噻吩基甲基叠氮(16.7mg,0.12mmol)，反应于室温下敞口反应8小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值94％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2-噻吩基甲基叠氮(16.7mg,0.12mmol)，反应于室温下敞口反应8小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率90％，ee值-95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点215–217℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝8.25min,t(minor)＝6.52min.]1H NMR(400MHz,CDCl3)δ8.89(s,1H),7.86(d,J＝8.8Hz,1H),7.70(d,J＝8.0Hz,1H),7.34(d,J＝8.8Hz,1H),7.21–7.14(m,3H),7.10–7.04(m,1H),7.02(dd,J1＝1.6Hz,J2＝0.4Hz,1H),6.85–6.71(m,4H),5.94(dd,J1＝3.2Hz,J2＝2.0Hz,1H),5.71(d,J＝3.2Hz,1H),5.34(d,J＝15.6Hz,1H),5.15(d,J＝15.6Hz,1H).13C NMR(100MHz,CDCl3)δ154.8,147.0,146.5,143.1,132.9,132.6,129.5,128.7,128.4,128.2,127.8,127.6,127.5,125.8,123.8,123.4,119.4,110.5,110.1,105.4,45.6.HRMS(ESI-TOF)Calcd for C23H18N3O2(M+H)+:368.1399；Found:368.1397.
R型产物：白色固体，熔点215–217℃；-95％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.61min,t(minor)＝8.62min.]1H NMR(400MHz,DMSO-d6)δ10.44(s,1H),8.04(d,J＝8.9Hz,1H),7.89(d,J＝8.1Hz,1H),7.49–7.12(m,9H),6.81(d,J＝8.3Hz,1H),6.76–6.71(m,1H),6.54(d,J＝3.5Hz,1H),5.51(d,J＝15.6Hz,1H),5.37(d,J＝15.6Hz,1H).13C NMR(101MHz,DMSO)δ154.5,144.2,136.8,132.7,132.2,131.2,128.7,128.5,128.4,127.8,127.6,127.5,127.4,126.8,126.6,125.2,123.3,122.5,118.2,105.5,45.9.HRMS(ESI-TOF)Calcdfor C23H18N3O2(M+H)+:368.1399；Found:368.1397.
实施例18
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2,6-二氟苄基叠氮(20.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值96％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入2,6-二氟苄基叠氮(20.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值-95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点246–248℃；96％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.91min,t(minor)＝5.49min.].1H NMR(400MHz,DMSO-d6)δ10.38(s,1H),7.96(d,J＝8.8Hz,1H),7.81(d,J＝8.0Hz,1H),7.45–7.37(m,2H),7.32(d,J＝8.8Hz,1H),7.24–7.11(m,6H),6.80–6.70(m,3H),5.47(d,J＝14.8Hz,1H),5.27(d,J＝14.8Hz,1H).13C NMR(100MHz,DMSO-d6)δ160.6(dd,JF-C,1＝249.6Hz,JF-C,2＝7.4Hz),154.7,144.2,132.5,132.1,131.2,130.8(t,JF-C＝10.5Hz),128.9,128.6,128.3,127.7,127.5,127.3,125.2,123.1,122.1,118.1,111.2(dd,JF-C,1＝18.9Hz,JF-C,2＝5.5Hz),110.4(t,JF-C＝18.4Hz),105.2,40.2.19F NMR(565MHz,DMSO-d6)δ-114.39.HRMS(ESI-TOF)Calcd for C25H18F2N3O(M+H)+:414.1418；Found:414.1419.
R型产物：白色固体，熔点246–248℃；96％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.58min,t(minor)＝6.09min.].1H NMR(400MHz,DMSO-d6)δ10.38(s,1H),7.96(d,J＝8.8Hz,1H),7.81(d,J＝8.0Hz,1H),7.45–7.37(m,2H),7.32(d,J＝8.8Hz,1H),7.24–7.11(m,6H),6.80–6.70(m,3H),5.47(d,J＝14.8Hz,1H),5.27(d,J＝14.8Hz,1H).13C NMR(100MHz,DMSO-d6)δ160.6(dd,JF-C,1＝249.6Hz,JF-C,2＝7.4Hz),154.7,144.2,132.5,132.1,131.2,130.8(t,JF-C＝10.5Hz),128.9,128.6,128.3,127.7,127.5,127.3,125.2,123.1,122.1,118.1,111.2(dd,JF-C,1＝18.9Hz,JF-C,2＝5.5Hz),110.4(t,JF-C＝18.4Hz),105.2,40.2.19F NMR(565MHz,DMSO-d6)δ-114.37.HRMS(ESI-TOF)Calcd for C25H18F2N3O(M+H)+:414.1418；Found:414.1419.
实施例19
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苯基烯丙基叠氮(19.1mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点103–105℃；95％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.51min,t(minor)＝7.53min.].1H NMR(400MHz,DMSO)δ10.41(s,1H),8.01(d,J＝8.8Hz,1H),7.91–7.86(m,1H),7.49–7.44(m,2H),7.36(d,J＝8.8Hz,1H),7.33–7.16(m,8H),7.15–7.11(m,2H),7.04–6.99(m,1H),6.22–6.10(m,2H),4.83(d,J＝4.8Hz,2H).13C NMR(100MHz,DMSO)δ154.5,144.3,135.7,132.93,132.85,132.1,131.3,128.9,128.54,128.47,127.9,127.6,127.5,126.2,125.2,123.3,123.1,122.7,118.2,105.8,49.8.HRMS(ESI-TOF)Calcdfor C27H22N3O(M+H)+:404.1763；Found:404.1762.
实施例20
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苯基高炔丙基叠氮(20.5mg,0.12mmol)，反应于室温下敞口反应3小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点96–98℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.26min,t(minor)＝6.57min.].1H NMR(400MHz,DMSO)δ10.48(s,1H),8.05(d,J＝8.8Hz,1H),7.91(d,J＝8.0Hz,1H),7.45–7.38(m,3H),7.34–7.13(m,10H),7.02(d,J＝8.0Hz,1H),4.31–4.16(m,2H),2.94–2.83(m,1H),2.80–2.69(m,1H).13C NMR(100MHz,DMSO)δ154.6,144.1,132.8,132.2,131.2,128.8,128.53,128.50,128.2,127.9,127.6,127.5,125.2,123.4,122.6,122.5,118.3,105.6,86.3,82.1,46.5,19.9.HRMS(ESI-TOF)Calcd for C28H22N3O(M+H)+:416.1763；Found:416.1761.
实施例21
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入对甲苯磺酰氧基乙基叠氮(28.9mg,0.12mmol)，反应于室温下敞口反应4小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率89％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点77–79℃；94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝50/50,v＝1.0mL·min–1,λ＝254nm),t(major)＝13.5min,t(minor)＝8.97min.]1H NMR(400MHz,CDCl3)δ8.77(s,1H),7.94(d,J＝8.8Hz,1H),7.82(d,J＝8.0Hz,1H),7.53(d,J＝8.4Hz,2H),7.40(d,J＝8.8Hz,1H),7.34–7.17(m,6H),7.00–6.95(m,1H),6.94–6.88(m,2H),6.85(d,J＝8.4Hz,1H),4.42–4.16(m,4H),2.36(s,3H).13CNMR(100MHz,CDCl3)δ154.6,146.2,145.3,132.82,132.77,132.2,130.0,129.6,128.8,128.51,128.47,128.1,127.98,127.95,125.9,124.1,123.1,119.3,105.0,66.8,47.1,21.7.HRMS(ESI-TOF)Calcd for C27H24N3O4S(M+H)+:486.1488；Found:486.1488.
实施例22
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入邻苯二甲酰氨基丙基叠氮(27.6mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率91％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点93–95℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝16.19min,t(minor)＝14.78min.].1H NMR(400MHz,CDCl3)δ8.50(s,1H),7.78(d,J＝8.8Hz,1H),7.75–7.64(m,5H),7.38–7.33(m,2H),7.30(d,J＝8.8Hz,1H),7.28–7.22(m,2H),7.03–6.92(m,4H),4.21–4.01(m,2H),3.72–3.56(m,2H),2.30–2.15(m,1H),2.14–2.00(m,1H).13CNMR(100MHz,CDCl3)δ168.2,154.2,146.3,134.1,132.9,132.5,131.9,130.1,128.7,128.5,128.4,128.0,127.8,127.6,125.9,124.0,123.4,123.2,119.1,105.8,46.6,35.4,28.5.HRMS(ESI-TOF)Calcd for C29H23N4O3(M+H)+:475.1770；Found:475.1770.
实施例23
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入叠氮乙酸苄酯(21.3mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率91％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点173–175℃；94％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝8.95min,t(minor)＝7.59min.].1H NMR(400MHz,DMSO)δ10.53(s,1H),8.03(d,J＝8.8Hz,1H),7.90(d,J＝8.0Hz,1H),7.44–7.39(m,2H),7.36(d,J＝8.8Hz,1H),7.32–7.16(m,8H),7.06–6.96(m,3H),5.40(d,J＝17.2Hz,1H),4.94–4.75(m,3H).13C NMR(100MHz,DMSO)δ166.3,154.3,144.1,135.1,132.4,131.0,129.7,128.6,128.4,128.2,127.9,127.8,127.7,127.4,125.3,123.4,123.1,118.2,104.9,66.4,49.0.HRMS(ESI-TOF)Calcd forC27H22N3O3(M+H)+:436.1661；Found:436.1661.
实施例24
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苯甲酰基丙基叠氮(22.7mg,0.12mmol)，反应于室温下敞口反应16小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率95％，ee值92％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点209–211℃；92％ee[大赛璐手性柱(IC-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝5.96min,t(minor)＝5.19min.].1H NMR(400MHz,DMSO)δ10.41(s,1H),8.02(d,J＝8.8Hz,1H),7.94–7.87(m,1H),7.76(d,J＝7.6Hz,2H),7.63–7.55(m,1H),7.51–7.40(m,4H),7.36(d,J＝8.8Hz,1H),7.33–7.26(m,2H),7.23–7.11(m,3H),7.05–6.96(m,1H),4.21–4.02(m,2H),3.03–2.82(m,2H),2.06–1.91(m,2H).13C NMR(100MHz,DMSO)δ198.7,154.5,144.1,136.3,133.1,132.9,132.1,131.4,128.9,128.6,128.5,127.9,127.73,127.70,127.4,125.2,123.4,122.5,118.3,105.8,47.1,34.7,23.7.HRMS(ESI-TOF)Calcd for C28H24N3O2(M+H)+:434.1896；Found:434.1892.
实施例25
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-氯丁基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率93％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点186–188℃；94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.84min,t(minor)＝4.02min.][α]D,25＝+55.7(c＝0.4,DMSO).1H NMR(400MHz,DMSO)δ10.41(s,1H),8.03(d,J＝8.8Hz,1H),7.94–7.89(m,1H),7.44–7.40(m,2H),7.37(d,J＝8.8Hz,1H),7.35–7.29(m,2H),7.22–7.13(m,3H),6.98–6.92(m,1H),4.13–3.95(m,2H),3.45(t,J＝6.4Hz,2H),1.76–1.52(m,4H).13C NMR(100MHz,DMSO)δ154.5,144.2,132.9,132.1,131.4,128.7,128.58,128.55,127.9,127.7,127.5,125.2,123.4,122.4,118.3,105.8,47.0,44.5,28.9,26.4.HRMS(ESI-TOF)Calcd for C22H21ClN3O(M+H)+:378.1373；Found:378.1373.
实施例26
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入4-叠氮氧杂环己烷(15.3mg,0.12mmol)，反应于室温下敞口反应6小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值92％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点276–277℃；92％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝7.16min,t(minor)＝5.30min.][α]D,25＝+38.9(c＝0.4,DMSO).1H NMR(400MHz,CDCl3)δ9.18(br,1H),7.95(d,J＝9.2Hz,1H),7.83(d,J＝7.8Hz,1H),7.51(d,J＝9.2Hz,1H),7.37–7.23(m,4H),7.04–6.90(m,4H),4.15–4.05(m,1H),4.05–3.97(m,1H),3.95–3.86(m,1H),3.29(td,J1＝12.0Hz,J2＝2.0Hz,1H),3.17(td,J1＝12.0Hz,J2＝2.0Hz,1H),2.54–2.41(m,1H),2.38–2.25(m,1H),2.23–2.13(m,1H),1.76–1.63(m,1H).13C NMR(100MHz,CDCl3)δ154.5,145.8,133.2,132.6,130.2,128.8,128.6,128.5,127.9,127.8,127.7,126.0,124.0,123.1,119.0,106.1,67.0,66.8,55.8,33.1,32.6.HRMS(ESI-TOF)Calcd forC23H22N3O2(M+H)+:372.1712；Found:372.1712.
实施例27
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-吲哚乙基叠氮(22.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率93％，ee值98％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入3-吲哚乙基叠氮(22.3mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点182–184℃；98％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝70/30,v＝0.8mL·min–1,λ＝254nm),t(major)＝8.20min,t(minor)＝7.66min.].1H NMR(400MHz,DMSO-d6)δ10.38(s,1H),7.96(d,J＝8.8Hz,1H),7.81(d,J＝8.0Hz,1H),7.45–7.37(m,2H),7.32(d,J＝8.8Hz,1H),7.24–7.11(m,6H),6.80–6.70(m,3H),5.47(d,J＝14.8Hz,1H),5.27(d,J＝14.8Hz,1H).13C NMR(100MHz,DMSO-d6)δ160.6(dd,JF-C,1＝249.6Hz,JF-C,2＝7.4Hz),154.7,144.2,132.5,132.1,131.2,130.8(t,JF-C＝10.5Hz),128.9,128.6,128.3,127.7,127.5,127.3,125.2,123.1,122.1,118.1,111.2(dd,JF-C,1＝18.9Hz,JF-C,2＝5.5Hz),110.4(t,JF-C＝18.4Hz),105.2,40.2.19F NMR(565MHz,DMSO-d6)δ-114.39.HRMS(ESI-TOF)Calcd for C25H18F2N3O(M+H)+:414.1418；Found:414.1419.
R型产物：白色固体，熔点182–184℃；-94％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝70/30,v＝0.8mL·min–1,λ＝254nm),t(major)＝7.20min,t(minor)＝7.87min.].1H NMR(400MHz,DMSO-d6)δ10.38(s,1H),7.96(d,J＝8.8Hz,1H),7.81(d,J＝8.0Hz,1H),7.45–7.37(m,2H),7.32(d,J＝8.8Hz,1H),7.24–7.11(m,6H),6.80–6.70(m,3H),5.47(d,J＝14.8Hz,1H),5.27(d,J＝14.8Hz,1H).13C NMR(100MHz,DMSO-d6)δ160.6(dd,JF-C,1＝249.6Hz,JF-C,2＝7.4Hz),154.7,144.2,132.5,132.1,131.2,130.8(t,JF-C＝10.5Hz),128.9,128.6,128.3,127.7,127.5,127.3,125.2,123.1,122.1,118.1,111.2(dd,JF-C,1＝18.9Hz,JF-C,2＝5.5Hz),110.4(t,JF-C＝18.4Hz),105.2,40.2.19F NMR(565MHz,DMSO-d6)δ-114.39.HRMS(ESI-TOF)Calcd for C25H18F2N3O(M+H)+:414.1418；Found:414.1419.
实施例28
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入二乙二醇叠氮(15.8mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值95％。
在反应管中称入1-苯乙炔基-2-萘酚(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入二乙二醇叠氮(15.8mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：浅色膏状；95％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝6.78min,t(minor)＝4.85min.].1H NMR(400MHz,CDCl3)δ8.70(br,1H),7.85(d,J＝9.2Hz,1H),7.74(d,J＝8.0Hz,1H),7.35–7.17(m,5H),6.99–6.84(m,4H),4.33–4.22(m,1H),4.12–4.02(m,1H),3.83–3.74(m,1H),3.65–3.58(m,1H),3.53–3.43(m,2H),3.40–3.27(m,2H),3.20(br,1H).13C NMR(100MHz,CDCl3)δ154.7,146.1,133.1,132.6,130.1,128.8,128.7,128.6,128.5,127.9,126.0,124.0,123.2,119.4,106.1,72.5,68.9,61.3,48.5.HRMS(ESI-TOF)Calcdfor C22H22N3O3(M+H)+:376.1661；Found:376.1660.
R型产物：浅色膏状；-95％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝4.86min,t(minor)＝6.78min.].1H NMR(400MHz,CDCl3)δ8.70(br,1H),7.85(d,J＝9.2Hz,1H),7.74(d,J＝8.0Hz,1H),7.35–7.17(m,5H),6.99–6.84(m,4H),4.33–4.22(m,1H),4.12–4.02(m,1H),3.83–3.74(m,1H),3.65–3.58(m,1H),3.53–3.43(m,2H),3.40–3.27(m,2H),3.20(br,1H).13C NMR(100MHz,CDCl3)δ154.7,146.1,133.1,132.6,130.1,128.8,128.7,128.6,128.5,127.9,126.0,124.0,123.2,119.4,106.1,72.5,68.9,61.3,48.5.HRMS(ESI-TOF)Calcdfor C22H22N3O3(M+H)+:376.1661；Found:376.1660.
实施例29
在反应管中称入1-(2-氟苯乙炔基)-2-萘酚(26.2mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率96％，ee值>99％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点190-192℃；>99％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝23.24min,t(minor)＝11.10min.].1H NMR(400MHz,DMSO)δ10.37(s,1H),7.92(d,J＝9.2Hz,1H),7.82–7.76(m,1H),7.43–7.37(m,1H),7.29(d,J＝8.8Hz,1H),7.27–7.04(m,8H),6.92–6.86(m,2H),6.83(d,J＝8.0Hz,1H),5.36(d,J＝15.2Hz,1H),5.26(d,J＝15.2Hz,1H).13C NMR(100MHz,DMSO)δ159.1(d,JF-C＝249.4Hz),154.4,141.0(d,JF-C＝2.1Hz),135.2,132.7,131.9,131.0,130.1(d,JF-C＝3.1Hz),130.0(d,JF-C＝7.9Hz),128.2,127.73,127.67,127.6,127.1,124.4(d,JF-C＝3.3Hz),123.0,122.4,119.2(d,JF-C＝14.3Hz),118.0,115.9(d,JF-C＝21.4Hz),105.4,51.6.19F NMR(565MHz,DMSO)δ-113.90.HRMS(ESI-TOF)Calcd for C25H19FN3O(M+H)+:396.1512；Found:396.1513.实施例30
在反应管中称入1-(4-氟苯乙炔基)-2-萘酚(26.2mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值97％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点211-213℃；97％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝9.67min,t(minor)＝9.22min.].1H NMR(400MHz,DMSO)δ10.44(s,1H),8.01(d,J＝8.8Hz,1H),7.86(d,J＝8.0Hz,1H),7.49–7.40(m,2H),7.35(d,J＝8.8Hz,1H),7.29–7.24(m,1H),7.23–7.17(m,1H),7.15–7.03(m,5H),6.91–6.85(m,2H),6.79(d,J＝8.0Hz,1H),5.27(d,J＝15.2Hz,1H),5.19(d,J＝15.2Hz,1H).13C NMR(100MHz,DMSO)δ161.5(d,JF-C＝244.5Hz),154.6,143.5,135.2,132.7,132.3,128.9,128.4,128.2,127.80(d,JF-C＝2.9Hz),127.77,127.72,127.65,127.5,127.2(d,JF-C＝8.1Hz),123.3,122.4,118.2,115.6(d,JF-C＝21.6Hz),105.4,51.4.19F NMR(565MHz,DMSO)δ-114.26.HRMS(ESI-TOF)Calcd forC25H19FN3O(M+H)+:396.1512；Found:396.1511.
实施例31
在反应管中称入1-(4-甲氧基苯乙炔基)-2-萘酚(27.4mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点212-214℃；95％ee[大赛璐手性柱(IE-3,0.46cm×15cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝9.67min,t(minor)＝9.22min.].1H NMR(400MHz,CDCl3)δ8.64(br,1H),7.93(d,J＝9.2Hz,1H),7.75(d,J＝8.0Hz,1H),7.38(d,J＝9.2Hz,1H),7.24–7.18(m,3H),7.07–6.96(m,4H),6.84–6.79(m,2H),6.68(d,J＝8.4Hz,1H),6.41(d,J＝8.8Hz,2H),5.30(d,J＝14.8Hz,1H),5.16(d,J＝14.8Hz,1H),3.60(s,3H).13C NMR(100MHz,CDCl3)δ159.1,154.5,146.5,134.1,132.8,132.5,128.7,128.6,128.4,128.1,127.4,127.1,126.3,123.8,123.4,122.4,119.3,113.8,105.9,55.0,53.1.HRMS(ESI-TOF)Calcd for C26H22N3O2(M+H)+:408.1712；Found:408.1709.
实施例32
在反应管中称入1-萘乙炔基-2-萘酚(29.4mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点186-188℃；95％ee[大赛璐手性柱(IE-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝6.31min,t(minor)＝5.67min].1H NMR(400MHz,CDCl3)δ9.60(br,1H),8.03(d,J＝8.8Hz,1H),7.83–7.76(m,2H),7.59(d,J＝9.2Hz,1H),7.33–7.03(m,9H),7.02–6.92(m,4H),6.70(d,J＝8.4Hz,1H),5.51(d,J＝14.8Hz,1H),5.28(d,J＝14.8Hz,1H).13C NMR(100MHz,CDCl3)δ154.9,146.6,133.9,132.8,132.7,132.5,128.64,128.56,128.4,128.1,128.01,127.98,127.7,127.3,127.2,126.9,125.7,125.6,124.9,123.7,123.3,123.1,119.4,105.7,53.2.HRMS(ESI-TOF)Calcd for C29H22N3O2(M+H)+:428.1763；Found:428.1768.
实施例33
在反应管中称入1-(2-噻吩乙炔基)-2-萘酚(25.0mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应8小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率89％，ee值87％。
反应式如下：
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产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点224-228℃；87％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝6.85min,t(minor)＝6.12min].1H NMR(600MHz,DMSO)δ10.42(br,1H),8.02(d,J＝9.0Hz,1H),7.87(d,J＝7.8Hz,1H),7.35(d,J＝9.0Hz,1H),7.33(d,J＝4.8Hz,1H),7.30–7.26(m,1H),7.25–7.20(m,1H),7.15–7.08(m,3H),6.94–6.90(m,2H),6.86–6.82(m,2H),6.65(dd,J1＝3.6Hz,J2＝0.6Hz,1H),5.33(d,J＝15.0Hz,1H),5.22(d,J＝15.0Hz,1H).13C NMR(100MHz,DMSO)δ154.7,140.7,135.1,133.1,132.7,132.4,128.4,128.2,127.74,127.71,127.69,127.5,127.4,125.3,123.3,123.1,122.5,118.1,104.7,51.5.HRMS(ESI-TOF)Calcd forC23H18N3OS(M+H)+:384.1171；Found:384.1171.
实施例34
在反应管中称入1-(1-环己烯乙炔基)-2-萘酚(24.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应5小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率76％，ee值97％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点204-206℃；97％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝6.76min,t(minor)＝4.67min].1H NMR(400MHz,CDCl3)δ8.28(br,1H),7.80(d,J＝8.8Hz,1H),7.67(d,J＝8.0Hz,1H),7.25(d,J＝8.8Hz,1H),7.20–7.14(m,1H),7.08–7.02(m,1H),6.97–6.85(m,3H),6.71–6.62(m,3H),5.98–5.94(m,1H),5.19(d,J＝14.8Hz,1H),5.02(d,J＝14.8Hz,1H),2.22–2.01(m,2H),1.91–1.70(m,2H),1.46–1.30(m,4H).13C NMR(100MHz,CDCl3)δ154.2,148.2,134.2,133.0,132.2,128.5,128.4,128.3,128.1,128.0,127.6,127.2,126.6,126.0,123.6,119.0,106.5,52.9,25.7,25.6,22.5,21.9.HRMS(ESI-TOF)Calcd forC25H24N3O2(M+H)+:382.1919；Found:382.1918.
实施例35
在反应管中称入1-(叔丁基乙炔基)-2-萘酚(22.4mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率92％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点264-266℃；95％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝3.67min,t(minor)＝3.46min].1H NMR(400MHz,DMSO)δ10.15(s,1H),7.94(d,J＝8.8Hz,1H),7.87–7.79(m,1H),7.30–7.19(m,3H),7.15–7.06(m,3H),6.88–6.81(m,2H),6.72(d,J＝8.0Hz,1H),5.02(d,J＝15.2Hz,1H),4.95(d,J＝15.2Hz,1H),1.08(s,9H).13C NMR(100MHz,DMSO)δ154.3,153.0,135.3,133.8,131.6,128.1,127.9,127.58,127.55,126.9,123.3,122.9,117.9,107.3,50.9,31.5,29.8.HRMS(ESI-TOF)Calcd for C23H24N3O2(M+H)+:358.1919；Found:358.1919.
实施例36
在反应管中称入1-(三甲基硅基乙炔基)-2-萘酚(24.0mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应12小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率92％，ee值86％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点223-225℃；86％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝4.00min,t(minor)＝3.44min].1H NMR(400MHz,DMSO)δ10.20(br,1H),7.94(d,J＝8.8Hz,1H),7.87–7.80(m,1H),7.33–7.22(m,3H),7.16–7.07(m,3H),6.94–6.86(m,2H),6.82–6.76(m,1H),5.25(d,J＝15.2Hz,1H),5.13(d,J＝15.2Hz,1H),-0.10(s,9H).13C NMR(100MHz,DMSO)δ154.2,144.4,138.5,135.6,133.7,131.5,128.2,128.1,127.8,127.5,127.4,126.8,123.1,123.0,117.8,106.6,50.6,-1.4.HRMS(ESI-TOF)Calcd for C22H24N3OSi(M+H)+:374.1689；Found:374.1689.
实施例37
在反应管中称入1-苯基乙炔基-3-甲基-2-萘酚(25.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率98.0％，ee值94％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点191-193℃；94％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝3.55min,t(minor)＝4.29min].1H NMR(400MHz,CDCl3)δ8.33(br,1H),7.80(s,1H),7.70(d,J＝8.4Hz,1H),7.33–7.27(m,2H),7.24–7.17(m,1H),7.10–7.04(m,1H),7.04–6.97(m,3H),6.95–6.79(m,5H),6.65(d,J＝8.4Hz,1H),5.30(d,J＝14.8Hz,1H),5.21(d,J＝14.8Hz,1H),2.58(s,3H).13C NMR(100MHz,CDCl3)δ153.6,146.6,134.0,131.9,131.5,129.7,128.7,128.6,128.4,128.1,127.7,127.5,127.3,126.5,125.7,123.7,123.1,105.3,53.1,17.5.HRMS(ESI-TOF)Calcd for C26H22N3O(M+H)+:392.1763；Found:392.1763.
实施例38
在反应管中称入1-苯基乙炔基-4-溴-2-萘酚(32.2mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应24小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率90.2％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点210-211℃；95％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝3.99min,t(minor)＝3.50min].1H NMR(400MHz,CDCl3)δ9.68(br,1H),8.12(d,J＝8.4Hz,1H),7.83(s,1H),7.30–7.25(m,1H),7.18(d,J＝7.6Hz,2H),7.06–6.95(m,4H),6.93–6.78(m,5H),6.58(d,J＝8.4Hz,1H),5.43(d,J＝14.8Hz,1H),5.15(d,J＝14.8Hz,1H).13C NMR(100MHz,CDCl3)δ154.5,146.7,133.6,133.2,129.1,128.6,128.44,128.43,128.2,128.1,127.9,127.4,127.3,127.1,127.0,125.6,125.0,123.73,123.68,105.8,53.4.HRMS(ESI-TOF)Calcd for C25H19BrN3O(M+H)+:456.0711,458.0691；Found:456.0711,458.0693.
实施例39
在反应管中称入1-苯基乙炔基-7-甲氧基-2-萘酚(27.4mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应1小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97.0％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点171-173℃；95％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝4.56min,t(minor)＝2.93min].1H NMR(600MHz,CDCl3)δ8.51(br,1H),7.85(d,J＝9.0Hz,1H),7.64(d,J＝9.0Hz,1H),7.34(d,J＝7.8Hz,2H),7.28–7.24(m,1H),7.08–7.04(m,1H),7.02–6.94(m,3H),6.94–6.90(m,2H),6.88–6.81(m,3H),5.85(d,J＝2.4Hz,1H),5.42(d,J＝15.0Hz,1H),5.15(d,J＝15.0Hz,1H),3.27(s,3H).13C NMR(150MHz,CDCl3)δ158.9,154.9,146.5,134.5,134.1,132.2,129.8,129.7,128.7,128.5,128.4,128.2,127.83,127.76,125.8,124.0,116.4,116.2,105.2,102.2,54.9,53.1.HRMS(ESI-TOF)Calcd for C26H22N3O2(M+H)+:408.1712；Found:408.1712.
实施例40
在反应管中称入5-苯基乙炔基-6-羟基喹啉(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应18小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率85.0％，ee值95％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点102-105℃；95％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝4.75min,t(minor)＝3.31min].1H NMR(400MHz,CDCl3)δ11.34(br,1H),8.57–8.44(m,1H),8.09(d,J＝9.2Hz,1H),7.66(d,J＝9.2Hz,1H),7.37(d,J＝7.2Hz,2H),7.05–6.86(m,8H),6.81–6.74(m,2H),5.55(d,J＝14.8Hz,1H),5.19(d,J＝14.8Hz,1H).13C NMR(100MHz,CDCl3)δ155.5,147.1,146.6,143.0,134.0,132.9,132.0,129.9,128.6,128.4,128.3,128.2,128.1,128.0,127.4,125.9,123.1,121.9,106.2,53.3.HRMS(ESI-TOF)Calcd for C24H19N4O(M+H)+:379.1559；Found:379.1559.
实施例41
在反应管中称入N-对甲苯磺酰基-5-苯基乙炔基-6-羟基四氢喹啉(40.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应18小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率93.0％，ee值97％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点209-211℃；97％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝15.91min,t(minor)＝7.31min].1H NMR(600MHz,DMSO)δ10.15(br,1H),7.74(d,J＝9.0Hz,1H),7.41–7.35(m,4H),7.32–7.27(m,3H),7.26–7.18(m,5H),7.02(d,J＝9.0Hz,1H),6.90(d,J＝7.2Hz,2H),5.43(d,J＝15.0Hz,1H),4.97(d,J＝15.0Hz,1H),3.66–3.60(m,1H),3.20–3.12(m,1H),2.27(s,3H),1.35–1.29(m,1H),1.10–1.02(m,1H),0.97–0.86(m,2H).13C NMR(150MHz,DMSO)δ153.5,143.48,143.46,136.0,135.0,132.1,131.0,129.8,128.8,128.74,128.71,128.6,128.4,128.1,128.0,127.6,126.7,124.8,114.0,113.1,51.6,45.2,23.3,20.9,19.6.HRMS(ESI-TOF)Calcd for C31H29N4O3S(M+H)+:537.1960；Found:537.1962.
实施例42
在反应管中称入1-苯基乙炔基-2-羟基四氢萘(24.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率88％，ee值99％。
在反应管中称入1-苯基乙炔基-2-羟基四氢萘(24.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率84％，ee值-96％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点233-235℃；99％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝5.56min].1H NMR(400MHz,DMSO)δ9.74(s,1H),7.52–7.46(m,2H),7.32–7.20(m,6H),7.10(d,J＝8.4Hz,1H),6.94–6.90(m,2H),6.87(d,J＝8.4Hz,1H),5.52(d,J＝14.8Hz,1H),4.99(d,J＝14.8Hz,1H),2.68–2.52(m,2H),1.80–1.67(m,1H),1.46–1.34(m,2H),1.28–1.18(m,2H),1.13–1.02(m,1H).13C NMR(100MHz,DMSO)δ153.3,143.3,137.1,135.0,132.1,131.5,130.0,128.7,128.4,128.3,128.0,127.8,127.6,124.7,113.4,113.0,51.7,28.3,26.3,22.3,22.0.HRMS(ESI-TOF)Calcd for C25H24N3O(M+H)+:382.1919；Found:382.1919.
R型产物：白色固体，熔点234-236℃；-96％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝6.26min].1H NMR(400MHz,DMSO)δ9.74(s,1H),7.52–7.46(m,2H),7.32–7.20(m,6H),7.10(d,J＝8.4Hz,1H),6.94–6.90(m,2H),6.87(d,J＝8.4Hz,1H),5.52(d,J＝14.8Hz,1H),4.99(d,J＝14.8Hz,1H),2.68–2.52(m,2H),1.80–1.67(m,1H),1.46–1.34(m,2H),1.28–1.18(m,2H),1.13–1.02(m,1H).13C NMR(100MHz,DMSO)δ153.3,143.3,137.1,135.0,132.1,131.5,130.0,128.7,128.4,128.3,128.0,127.8,127.6,124.7,113.4,113.0,51.7,28.3,26.3,22.3,22.0.HRMS(ESI-TOF)Calcd for C25H24N3O(M+H)+:382.1919；Found:382.1919.
实施例43
在反应管中称入1-苯基乙炔基-6-氯-2-苯酚(22.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应16小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率83％，ee值95％。
在反应管中称入1-苯基乙炔基-6-氯-2-苯酚(22.8mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应16小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率80％，ee值-97％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点260-262℃；95％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝7.77min,t(minor)＝4.67min].1H NMR(400MHz,DMSO)δ10.56(br,1H),7.51–7.45(m,2H),7.43–7.37(m,1H),7.35–7.29(m,2H),7.28–7.21(m,4H),7.07–6.98(m,4H),5.41(d,J＝15.2Hz,1H),5.24(d,J＝15.2Hz,1H).13C NMR(100MHz,DMSO)δ157.5,144.0,135.0,134.5,132.7,131.2,128.7,128.4,127.93,127.88,127.8,125.2,120.1,114.8,113.5,51.6.HRMS(ESI-TOF)Calcd for C21H17ClN3O(M+H)+:362.1060；Found:362.1059.
R型产物：白色固体，熔点259-262℃；-97％ee[大赛璐手性柱(AD-H,0.46cm×25cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝4.70min,t(minor)＝7.67min].1H NMR(400MHz,DMSO)δ10.56(br,1H),7.51–7.45(m,2H),7.43–7.37(m,1H),7.35–7.29(m,2H),7.28–7.21(m,4H),7.07–6.98(m,4H),5.41(d,J＝15.2Hz,1H),5.24(d,J＝15.2Hz,1H).13C NMR(100MHz,DMSO)δ157.5,144.0,135.0,134.5,132.7,131.2,128.7,128.4,127.93,127.88,127.8,125.2,120.1,114.8,113.5,51.6.HRMS(ESI-TOF)Calcd for C21H17ClN3O(M+H)+:362.1060；Found:362.1059.
实施例44
在反应管中称入1-苯基乙炔基-6-乙烯基-2-苯酚(22.0mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应1小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率97％，ee值99％。
在反应管中称入1-苯基乙炔基-6-乙烯基-2-苯酚(22.0mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg，0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16.0mg,0.12mmol)，反应于室温下敞口反应1小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率92％，ee值-97％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点140-142℃；99％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝6.94min,t(minor)＝9.06min].1H NMR(600MHz,CDCl3)δ7.65–7.58(m,2H),7.25–7.11(m,7H),7.04–6.94(m,3H),5.99–5.89(m,2H),5.38–5.24(m,3H),4.84(d,J＝10.8Hz,1H),3.91(s,3H).13CNMR(150MHz,CDCl3)δ146.3,145.5,144.3,134.8,133.0,131.5,131.3,128.5,128.4,128.3,128.1,128.0,127.7,126.1,117.3,115.2,112.8,112.4,56.2,52.6.HRMS(ESI-TOF)Calcd for C24H22N3O2(M+H)+:384.1712；Found:384.1713.
R型产物：白色固体，熔点141-142℃；-97％ee[大赛璐手性柱(IC-3,0.46cm×15cm),n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm,t(major)＝8.94min,t(minor)＝7.06min].1H NMR(600MHz,CDCl3)δ7.65–7.58(m,2H),7.25–7.11(m,7H),7.04–6.94(m,3H),5.99–5.89(m,2H),5.38–5.24(m,3H),4.84(d,J＝10.8Hz,1H),3.91(s,3H).13CNMR(150MHz,CDCl3)δ146.3,145.5,144.3,134.8,133.0,131.5,131.3,128.5,128.4,128.3,128.1,128.0,127.7,126.1,117.3,115.2,112.8,112.4,56.2,52.6.HRMS(ESI-TOF)Calcd for C24H22N3O2(M+H)+:384.1712；Found:384.1713.
实施例45
在反应管中称入1-苯乙炔基-2-萘胺(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值76％。
在反应管中称入1-苯乙炔基-2-萘胺(24.5mg,0.1mmol)、[Rh(cod)(OH)]2(0.5mg,0.001mmol)，(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂(1.1mg,0.002mmol)，加入二氯甲烷(1mL)，随后加入苄基叠氮(16mg,0.12mmol)，反应于室温下敞口反应2小时，TLC检测反应转化完全，反应液直接通过硅胶柱层析分离(洗脱剂为石油醚：乙酸乙酯＝3：1)可得产物，收率99％，ee值-76％。
反应式如下：
产物的物理性质和谱图数据如下。
S型产物：白色固体，熔点179–181℃；76％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝13.99min,t(minor)＝11.89min.]1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.8Hz,1H),7.79–7.74(m,1H),7.67–7.60(m,2H),7.28–7.11(m,7H),7.11–7.05(m,2H),6.94–6.83(m,4H),5.37(d,J＝14.8Hz,1H),5.02(d,J＝14.8Hz,1H),3.45(br,2H).13C NMR(100MHz,CDCl3)δ146.0,144.1,134.6,133.4,131.9,130.9,128.7,128.53,128.47,128.4,128.2,128.0,127.94,127.91,125.8,123.0,122.6,117.9,103.1,52.7.HRMS(ESI-TOF)Calcd forC25H21N4(M+H)+:377.1766；Found:377.1766.
R型产物：白色固体，熔点179–180℃；-76％ee[大赛璐手性柱(AD-H,0.46cm×25cm),流动相(n-hexane/2-propanol＝60/40,v＝1.0mL·min–1,λ＝254nm),t(major)＝11.69min,t(minor)＝14.06min.]1H NMR(400MHz,CDCl3)δ7.82(d,J＝8.8Hz,1H),7.79–7.74(m,1H),7.67–7.60(m,2H),7.28–7.11(m,7H),7.11–7.05(m,2H),6.94–6.83(m,4H),5.38(d,J＝14.8Hz,1H),5.02(d,J＝14.8Hz,1H),3.45(br,2H).13C NMR(100MHz,CDCl3)δ146.0,144.1,134.6,133.4,131.9,130.9,128.7,128.53,128.47,128.4,128.2,128.01,127.95,127.9,125.8,123.0,122.6,117.9,103.1,52.7.
HRMS(ESI-TOF)Calcd for C25H21N4(M+H)+:377.1766；Found:377.1766.

Claims (6)

1.一种轴手性芳基三氮唑类化合物的制备方法，其特征在于，包括如下步骤：在金属催化剂和手性亚磷酰胺配体的协同催化下，各类未取代或单取代或多取代的1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物，与有机叠氮类化合物在溶剂中发生区域和轴手性对映选择性的环加成反应；反应完成后，经后处理得到所述的单一轴手性构型的芳基三氮唑类化合物；
所述的1-炔基2-萘酚类化合物的结构如式(Ⅶ)所示：
所述的邻炔基苯酚类化合物的结构如式(Ⅷ)所示：
所述的1-炔基-2-萘胺类化合物的结构如式(Ⅸ)所示：
所述的有机叠氮类化合物结构如式(Ⅹ)所示：
R6-N3 (Ⅹ)；
所述的S构型的轴手性芳基三氮唑的结构如式(Ⅰ)、(Ⅱ)或(Ⅲ)所示：
所述的R构型的轴手性芳基三氮唑的结构如式(IV)、(Ⅴ)或(Ⅵ)所示
式(Ⅰ)～式(Ⅹ)中，R1、R4为未取代或带各种取代基的苯基、2-萘基、芳杂环、环己烯基、正丁基、环丙基、羟基取代的烷基、叔丁基以及三甲基硅基；
所述的苯环上的取代基选自甲基、戊基、甲氧基或卤素；
所述的芳杂环选自2-噻吩基；
R2、R3为任意取代位置的氢、苯基、溴、甲氧基、醛基、氰基；
式(Ⅱ)、(V)和(Ⅷ)中，
R5为叔丁基、羟甲基、异丙氧基、乙烯基、酰基乙烯基、卤素；
R6为未被取代或带有各种取代基的苯基、2-萘基、芳杂环、未被取代或带各种取代基的烷基；
所述的苯基上的取代基选自卤素、甲基、硝基、氰基、三氟甲基、甲氧基、乙炔基、乙酰基、酯基、羟基、氨基；
所述的芳杂环基团选自2-吡啶基、5-吲哚基；
所述烷基上的取代基选自苯基、呋喃基、噻吩基、烯基、炔基、吲哚基、羟基、氨基、酯基、羰基；
式(Ⅰ)中，X为碳原子或氮原子；
式(IV)中，X为碳原子或氮原子；
式(Ⅶ)中，X为碳原子或氮原子；
式(Ⅱ)中，环状结构为六元碳环或哌啶环；
式(Ⅴ)中，环状结构为六元碳环或哌啶环；
式(Ⅷ)中，环状结构为六元碳环或哌啶环；
所述的金属催化剂为羟基(1,5-环辛二烯)铑(I)二聚体[Rh(cod)(OH)]2；
所述的手性配体为(S)-(+)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂或(R)-(-)-(3,5-二氧杂-4-磷环庚并[2,1-a；3,4-a']二萘-4-基)-5氢-二苯并[b,f]氮杂/>
2.根据权利要求1所述的轴手性芳基三氮唑类化合物的制备方法，其特征在于，所述的1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物与有机叠氮化合物的摩尔比为1:1.1～1.3。
3.根据权利要求1所述的轴手性芳基三氮唑类化合物的制备方法，其特征在于，所述的溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、乙酸乙酯、乙醚、1,4-二氧六环、甲醇、乙醇、四氢呋喃、甲苯、水的一种或混合溶剂。
4.根据权利要求1所述的轴手性芳基三氮唑类化合物的制备方法，其特征在于，所述的金属催化剂以1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物计，用量的摩尔比为0.5～1.5％。
5.根据权利要求1所述的轴手性芳基三氮唑类化合物的制备方法，其特征在于，所述的手性配体以1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物计，以1-炔基-2-萘酚、邻炔基苯酚或1-炔基-2-萘胺类化合物计，用量的摩尔比为1～3％。
6.根据权利要求1所述的轴手性芳基三氮唑类化合物的制备方法，其特征在于，反应温度为-20～25℃。
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