一类手性芳香胺类化合物及其制备方法转让专利
申请号 : CN201711129805.6
文献号 : CN107814729B
文献日 : 2019-11-22
发明人 : 郭昌 , 常西浩 , 张庆林
申请人 : 中国科学技术大学
摘要 :
本发明公开了一类手性芳香胺类化合物及其制备方法，特征是在碱性条件下，式1类化合物和式II类化合物反应：其中R1为苯基、甲基、甲氧基、乙氧基、异丙氧基、苄氧基；R2为甲基、乙基、丙基、丁基；R3为氢或甲基；R4为氢、苯基或甲基；R5为甲基、乙基、丙基、丁基、苄基、苯基；R6为氢或甲基；得到具有相应结构式的手性芳香胺类化合物或其对映体、消旋体、非对映异构体或同位素标记的相应产物芳香胺类化合物。采用本发明方法易制得高光学纯度(ee值>99％)的手性芳香胺类化合物，在生物活性、材料、手性配体和手性催化剂等领域具有广泛的应用。本发明为开发一类新型不对称催化反应的催化剂奠定了基础，具有经济实用性和工业应用前景。
权利要求 :
1.一类手性芳香胺类化合物的制备方法，其特征在于：
在空气环境下，以手性苯酚类化合物及其衍生物即式1类化合物作为反应底物，卤代酰胺类化合物即式II类化合物作为烷基化试剂，将式1类化合物与式II类化合物按摩尔比1:
1-6，式1类化合物与碱按摩尔比1:1-6，以及按式1类化合物0.1倍当量的碘化钾，加入到有机溶剂中，在50-100℃进行烷基化反应12-48小时，薄层色谱点板确定反应终点；
再在原反应体系中加入按式1类化合物10-30倍当量的碱，90-150℃反应3-36小时，薄层色谱点板确定反应终点，然后经过柱层析即得到相应的手性芳香胺类化合物，或其对映体、消旋体、非对映异构体或同位素标记的相应产物：式中的手性芳香胺类化合物中的取代基R1为苯基、甲基、甲氧基、乙氧基、异丙氧基、苄氧基；R2为甲基、乙基、丙基、丁基；R3为氢或甲基；R4为氢、苯基或甲基；R5为甲基、乙基、丙基、丁基、苄基、苯基；R6为氢或甲基。
2.如权利要求1所述手性芳香胺类化合物的制备方法，特征在于所述有机溶剂为苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、丙酮、乙腈、1,4-二氧六环、四氢呋喃、1,2-二氯乙烷、乙醚、甲醇、乙醇，N,N-二甲基甲酰胺或二甲基亚砜。
3.如权利要求1所述手性芳香胺类化合物的制备方法，特征在于所述的碱为叔丁醇钠、叔丁醇钾、碳酸氢钠、碳酸氢钾、碳酸钾、碳酸钠、碳酸铯、碳酸锶、氢氧化钠、氢氧化钾、正丁基锂、异丁基锂或三乙胺。
4.如权利要求1所述手性芳香胺类化合物的制备方法，特征在于所述卤代酰胺类化合物即式II化合物采用在二氯甲烷中将卤代酰基类化合物和各种取代基取代的胺类化合物在碱的作用下制备：式中，R7、R8、R9取代基对应权利要求1中式II化合物中的取代基；R9NH2选自14N或同位素15N标记的胺类化合物；所述卤代酰基类化合物与各种取代基取代的胺类化合物的摩尔比为1:1-10；所述的碱为氢氧化钠、氢氧化钾、甲醇钠、碳酸钠、碳酸钾、碳酸铯、氨水、二乙胺或三乙胺，所述卤代酰基类化合物与碱的摩尔比为1:1-10。
5.如权利要求1所述手性芳香胺类化合物的制备方法，特征在于所述卤代酰胺类化合物即式II化合物当采用同位素15N标记的卤代酰胺类化合物作为烷基化试剂，即得到相应的同位素15N标记的手性芳香胺类化合物。
说明书 :
一类手性芳香胺类化合物及其制备方法
技术领域
[0001] 本发明属于有机合成方向芳香胺类化合物制备方法技术领域，具体涉及手性芳香胺类化合物及其制备方法。
背景技术
[0002] 手性芳香胺类化合物是一些天然产物、生物活性化合物、材料、手性配体和手性催化剂的重要结构单元。在生物活性领域，如(-)-streptonigrin这类天然产物化合物(Rao,K.V.,Biemann,K.&Woodward R.B.J.Am.Chem.Soc.1963,85,2532-2533)，其含有与轴手性相连的苯酚与芳基胺片段，并由特殊的手性芳香胺骨架相连，这一独特的结构使其成为具有显著生物活性的抗生素，因而这一家族化合物有着相当好的抗癌、抗细菌、真菌、线虫、病毒等广泛的生物活性。在催化领域，手性芳香胺类化合物已广泛用作不对称合成中强大的手性配体或助剂。下面是部分手性芳香胺骨架的手性配体实例：
[0003]
[0004] 在过渡金属络合物催化中，以芳香亚胺结构作为骨架的配体也有成功的应用，例如Carreira等基于具有手性的联萘胺骨架的配体与金属钛形成的络合物在催化不对称Aldol加成反应中表现出良好的催化性能(Carreira,E.M.,Singer,R.A.&Lee,W.J.Am.Chem.Soc.1994,116,8837-8838)。周其林等通过另一具有手性螺芳香胺手性配体，成功应用于铜催化下高对映选择性卡宾插入硅氢键的反应中(Zhang,Y.-Z.,Zhu,S.-F.,Wang,L.-X.&Zhou,Q.-L.Angew.Chem.Int.Ed.2008,47,8496-8498)。关于这些生物活性化合物及手性配体类化合物的合成关键在芳香胺骨架的构筑上，目前报道的芳香胺的制备方法主要有金属催化的硝基还原，水合肼还原法等。但这些方法均仅局限于合成外消旋的芳香胺产物，仅有的几例通过铜催化的氧化交叉偶联，及金属介入的交叉偶联制备手性芳香类化合物的合成，所用原料β-萘胺具有毒性较大缺点，环境影响较大，且亦只能得到外消旋的产物，必须通过进一步的手性拆分才能得到手性芳香胺。然而，欲获得光学纯的手性芳香胺化合物，通常需要经过消旋体的拆分，过程繁琐且不经济环保。因此，开发简单、易得的合成手性芳香胺的制备方法是非常有必要的。
发明内容
[0005] 本发明的目的是提供一类手性芳香胺类化合物及其制备方法，以发展一类通过简单、易得的原料经过烷基化、不对称重排反应实现手性芳香胺类化合物的制备，从而克服现有技术的上述缺陷。
[0006] 本发明的手性芳香胺类化合物的制备方法，其特征在于：采取两步法，具体操作步骤如下：
[0007] 在空气环境下，以手性苯酚类化合物及其衍生物即式1类化合物作为反应底物，卤代酰胺类化合物即式II类化合物作为烷基化试剂，将式1类化合物与式II类化合物按摩尔比1:1-6，式1类化合物与碱按摩尔比为1:1-6，以及按式1类化合物0.1倍当量的碘化钾，加入到有机溶剂中，在50-100℃反应温度条件下进行烷基化反应12-48小时，薄层色谱点板确定反应终点；
[0008] 再在原反应体系中加入按式1类化合物10-30倍当量的碱，90-150℃反应温度下在原来反应体系中反应3-36小时，薄层色谱点板确定反应终点，然后经过柱层析即得到相应的手性芳香胺类化合物，或其对映体、消旋体、非对映异构体或同位素标记的相应产物：
[0009]
[0010]
[0011] 式中的手性芳香胺类化合物中的取代基R1为苯基、甲基、甲氧基、乙氧基、异丙氧基、苄氧基；R2为甲基、乙基、丙基、丁基；R3为氢或甲基；R4为氢、苯基或甲基；R5为甲基、乙基、丙基、丁基、苄基、苯基；R6为氢或甲基。
[0012] 所述有机溶剂为苯、甲苯、二甲苯、二氯甲烷、氯仿、四氯化碳、丙酮、乙腈、1,4-二氧六环、四氢呋喃、1,2-二氯乙烷、乙醚、甲醇、乙醇，N,N-二甲基甲酰胺或二甲基亚砜；
[0013] 所述的碱为叔丁醇钠、叔丁醇钾、碳酸氢钠、碳酸氢钾、碳酸钾、碳酸钠、碳酸铯、碳酸锶、氢氧化钠、氢氧化钾、正丁基锂、异丁基锂或三乙胺。
[0014] 所述的卤代酰胺类化合物即式II类化合物为14N或同位素15N标记的卤代酰胺类化合物；可采用在二氯甲烷中将卤代酰基类化合物和各种取代基取代的胺类化合物在碱的作用下制备：
[0015]
[0016] 式中，R7、R8、R9取代基对应权利要求1中式II化合物中的取代基；R9NH2选自14N或同位素15N标记的胺类化合物；所述卤代酰基类化合物与各种取代基取代的胺类化合物的摩尔比为1:1-10；所述的碱为氢氧化钠、氢氧化钾、甲醇钠、碳酸钠、碳酸钾、碳酸铯、氨水、二乙胺或三乙胺，所述卤代酰基类化合物与碱的摩尔比为1:1-10；
[0017] 所述卤代酰胺类化合物即式II化合物当采用同位素15N标记的卤代酰胺类化合物15
作为烷基化试剂，即得到相应的同位素 N标记的手性芳香胺类化合物。
作为烷基化试剂，即得到相应的同位素 N标记的手性芳香胺类化合物。
[0018] 本发明的采用上述方法制备的手性芳香胺类化合物，其特征在于是具有如下化学结构式的化合物或其对映体、消旋体、非对映异构体或同位素标记的相应产物：
[0019]
[0020] 其中的手性芳香胺类化合物中的取代基R1为苯基、甲基、甲氧基、乙氧基、异丙氧基、苄氧基；R2为甲基、乙基、丙基、丁基；R3为氢或甲基；R4为氢、苯基或甲基；R5为甲基、乙基、丙基、丁基、苄基、苯基；R6为氢或甲基。
[0021] 上述本发明手性芳香胺化合物的合成方法，采取了两步法，先是以手性苯酚类化合物及其衍生物作为反应底物，卤代酰胺类化合物作为烷基化试剂，碘化钾作为添加剂，在碱的作用下进行烷基化反应；再在碱性加热的条件下，进行不对称重排反应，所得产物经水解后即得到手性芳香胺类化合物；而现有的制备手性芳香胺的合成方法，不仅要使用毒性较大的β-萘胺作为起始原料，通过偶联反应制备消旋的芳香胺化合物，然后要经过复杂的手性拆分才能得到手性芳香胺化合物。而本发明采取简单的“一锅两步”合成方法，反应中间体无需处理，实现了手性芳香胺类化合物的合成，简化了传统繁琐的合成步骤，简便易行，易于操作，且底物适用性非常广，能耐受多种官能团。本发明也成功实现了通过试剂控制反应选择性，选择性制备手性单芳基胺类化合物和双胺基类化合物；且本发明采取的是无金属催化体系，既经济环保，又避免了参与一些药物分子合成过程中的金属残留。本发明不仅成功的实现了手性芳香胺类化合物的合成，而且简化了传统的合成方法，很容易制得高产率、高光学纯度(ee值>99％)的手性芳香胺类化合物。该芳香胺类化合物，可通过进一步衍生制备成消旋或手性的芳香亚胺类配体，用作不对称催化反应的催化剂。本发明为开发一类新型不对称催化反应的催化剂奠定了基础，具有经济实用性和工业应用前景。
具体实施方式
[0022] 实施例1：(R)-2'-氨基-[1,1'-联萘]-2-醇的制备(3a)
[0023]
[0024] 在空气环境下，在反应管中加入1a(0.2mmol),2e(0.3mmol),碳酸钾(0.3mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失后，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钾(2.0mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3a。该类发明简化了传统繁琐的合成步骤，简便易行，易于操作。
[0025] 产物收率72％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.92(d,J＝9.0Hz,1H),7.87(d,J＝8.0Hz,1H),7.84(d,J＝8.8Hz,1H),7.80(d,J＝7.8Hz,1H),7.39–7.31(m,2H),
7.30–7.20(m,3H),7.17(d,J＝8.4Hz,1H),7.13(d,J＝8.8Hz,1H),7.04(d,J＝8.0Hz,1H),
5.14(br s,1H),3.72(br s,2H).13C NMR(101MHz,CDCl3)δ151.95,143.87,134.25,133.32,
130.74,130.49,129.64,128.49,128.44,128.38,127.45,127.10,124.67,123.86,123.78,
122.89,118.30,117.84,114.39,108.64.ATR-FTIR(cm-1):3479,2928,1621,1403,1143,+ 20
819.ESI-MS:calculated[C20H15NO+H]:286.1226,found:286.1239.[α] D＝+35.1(c＝
0.58,CH2Cl2).HPLC：(OJ-H,hexane/i-PrOH＝80/20,detector:254nm,flow rate:1mL/min),t1(major)＝16.6min,t2(minor)＝22.8min.。
7.30–7.20(m,3H),7.17(d,J＝8.4Hz,1H),7.13(d,J＝8.8Hz,1H),7.04(d,J＝8.0Hz,1H),
5.14(br s,1H),3.72(br s,2H).13C NMR(101MHz,CDCl3)δ151.95,143.87,134.25,133.32,
130.74,130.49,129.64,128.49,128.44,128.38,127.45,127.10,124.67,123.86,123.78,
122.89,118.30,117.84,114.39,108.64.ATR-FTIR(cm-1):3479,2928,1621,1403,1143,+ 20
819.ESI-MS:calculated[C20H15NO+H]:286.1226,found:286.1239.[α] D＝+35.1(c＝
0.58,CH2Cl2).HPLC：(OJ-H,hexane/i-PrOH＝80/20,detector:254nm,flow rate:1mL/min),t1(major)＝16.6min,t2(minor)＝22.8min.。
[0026] 实施例2：(R)-2'-苯基-[1,1'-联萘]-2-胺的制备(3b)
[0027]
[0028] 在空气环境下，在反应管中加入1b(0.2mmol),2b(0.3mmol),碳酸钾(0.3mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1b完全消失后，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钠(6mmol),然后放入预先升温至130℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3b。
[0029] 产物收率95％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ8.02(d,J＝8.5Hz,1H),7.95(d,J＝8.2Hz,1H),7.71–7.62(m,3H),7.47(t,J＝7.3Hz,1H),7.34–7.25(m,2H),7.21–
7.16(m,2H),7.16–7.10(m,2H),7.06–7.01(m,3H),6.98(d,J＝8.4Hz,1H),6.90(d,J＝
8.7Hz,1H),3.48(br s,2H).13C NMR(101MHz,CDCl3)δ142.13,141.54,140.61,134.67,
133.44,132.88,131.75,129.11,128.81,128.63,128.22,128.02,127.88,127.60,126.93,-1
126.78,126.56,126.51,126.22,124.61,122.12,117.96,116.32.ATR-FTIR(cm ):3473,
3382,3054,2925,2854,1620,1513,1380,764,700.ESI-MS:calculated[C26H19N+H]+:
346.1590,found:346.1595.[α]20D＝+25.9(c＝0.91,CH2Cl2).HPLC：(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(minor)＝11.4min,t2(major)＝
14.8min.。
7.16(m,2H),7.16–7.10(m,2H),7.06–7.01(m,3H),6.98(d,J＝8.4Hz,1H),6.90(d,J＝
8.7Hz,1H),3.48(br s,2H).13C NMR(101MHz,CDCl3)δ142.13,141.54,140.61,134.67,
133.44,132.88,131.75,129.11,128.81,128.63,128.22,128.02,127.88,127.60,126.93,-1
126.78,126.56,126.51,126.22,124.61,122.12,117.96,116.32.ATR-FTIR(cm ):3473,
3382,3054,2925,2854,1620,1513,1380,764,700.ESI-MS:calculated[C26H19N+H]+:
346.1590,found:346.1595.[α]20D＝+25.9(c＝0.91,CH2Cl2).HPLC：(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(minor)＝11.4min,t2(major)＝
14.8min.。
[0030] 实施例3：(R)-2'-甲基-[1,1'-联萘]-2-胺的制备(3c)
[0031]
[0032] (R)-2'-甲基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3c，制备方法与实施例2相同。
[0033] 产物收率96％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.85(m,2H),7.78(d,J＝8.5Hz,2H),7.52(d,J＝8.4Hz,1H),7.42–7.36(m,1H),7.25–7.18(m,3H),7.13(t,J＝7.5Hz,1H),7.09(d,J＝8.7Hz,1H),6.88(d,J＝8.3Hz,1H),3.46(br s,2H),2.13(s,3H)13
. C NMR(101MHz,CDCl3)δ141.65,136.15,133.84,132.89,132.73,132.16,129.21,
129.04,128.27,128.17,128.15,128.10,126.65,126.53,125.66,125.30,124.11,122.33,
118.20,116.37,20.11.ATR-FTIR(cm-1):3475,3381,3052,2922,2853,1619,1512,1380,
813,746.ESI-MS:calculated[C21H17N+H]+:284.1433,found:284.1443.[α]20D＝+5.8(c＝
0.96,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝8.7min,t2(minor)＝10.2min.。
. C NMR(101MHz,CDCl3)δ141.65,136.15,133.84,132.89,132.73,132.16,129.21,
129.04,128.27,128.17,128.15,128.10,126.65,126.53,125.66,125.30,124.11,122.33,
118.20,116.37,20.11.ATR-FTIR(cm-1):3475,3381,3052,2922,2853,1619,1512,1380,
813,746.ESI-MS:calculated[C21H17N+H]+:284.1433,found:284.1443.[α]20D＝+5.8(c＝
0.96,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝8.7min,t2(minor)＝10.2min.。
[0034] 实施例4：(R)-2'-甲氧基-[1,1'-联萘]-2-胺的制备(3d)
[0035]
[0036] (R)-2'-甲氧基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3d，制备方法与实施例2相同。
[0037] 产物收率90％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.99(d,J＝9.1Hz,1H),7.87(d,J＝8.1Hz,1H),7.81–7.74(m,2H),7.46(d,J＝9.0Hz,1H),7.33(t,J＝7.3Hz,1H),
7.26–7.09(m,5H),6.97(d,J＝8.3Hz,1H),3.77(s,3H),3.11(br s,2H).13C NMR(101MHz,CDCl3)δ155.55,141.58,134.24,133.75,130.17,129.68,129.16,128.52,128.19,128.14,
127.05,126.44,125.14,124.49,124.05,122.42,118.82,118.44,114.44,56.97.ATR-FTIR(cm-1):3471,3380,3054,2929,1620,1506,1261,1707,811,748.ESI-MS:calculated[C21H17NO+H]+:300.1382,found:300.1392.[α]20D＝+91.5(c＝0.98,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝6.1min,t2(minor)＝12.1min.。
7.26–7.09(m,5H),6.97(d,J＝8.3Hz,1H),3.77(s,3H),3.11(br s,2H).13C NMR(101MHz,CDCl3)δ155.55,141.58,134.24,133.75,130.17,129.68,129.16,128.52,128.19,128.14,
127.05,126.44,125.14,124.49,124.05,122.42,118.82,118.44,114.44,56.97.ATR-FTIR(cm-1):3471,3380,3054,2929,1620,1506,1261,1707,811,748.ESI-MS:calculated[C21H17NO+H]+:300.1382,found:300.1392.[α]20D＝+91.5(c＝0.98,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝6.1min,t2(minor)＝12.1min.。
[0038] 实施例5：(R)-2'-乙氧基-[1,1'-联萘]-2-胺的制备(3e)
[0039]
[0040] (R)-2'-乙氧基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3e，制备方法与实施例2相同。
[0041] 产物收率89％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.95(d,J＝9.0Hz,1H),7.86(d,J＝8.1Hz,1H),7.76(d,J＝8.5Hz,2H),7.43(d,J＝9.0Hz,1H),7.33(t,J＝7.1Hz,
1H),7.26–7.08(m,5H),6.98(d,J＝8.3Hz,1H),4.09–3.96(m,2H),3.21(br s,2H),1.06(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ154.88,142.16,134.34,133.83,129.90,129.85,
128.97,128.26,128.15,128.03,126.91,126.25,125.26,124.53,124.10,122.12,120.15,
118.29,116.54,114.13,65.50,15.14.ATR-FTIR(cm-1):3471,3381,3055,2978,2924,1620,
1592,1506,1235,810,748.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:314.1543.[α]20D＝+82.5(c＝1.08,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝6.9min,t2(minor)＝11.4min.。
1H),7.26–7.08(m,5H),6.98(d,J＝8.3Hz,1H),4.09–3.96(m,2H),3.21(br s,2H),1.06(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ154.88,142.16,134.34,133.83,129.90,129.85,
128.97,128.26,128.15,128.03,126.91,126.25,125.26,124.53,124.10,122.12,120.15,
118.29,116.54,114.13,65.50,15.14.ATR-FTIR(cm-1):3471,3381,3055,2978,2924,1620,
1592,1506,1235,810,748.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:314.1543.[α]20D＝+82.5(c＝1.08,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝6.9min,t2(minor)＝11.4min.。
[0042] 实施例6：(R)-2'-异丙氧基-[1,1'-联萘]-2-胺的制备(3f)
[0043]
[0044] (R)-2'-异丙氧基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3f，制备方法与实施例2相同。
[0045] 产物收率95％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.92(d,J＝9.0Hz,1H),7.86(d,J＝8.1Hz,1H),7.76(d,J＝8.5Hz,2H),7.41(d,J＝9.0Hz,1H),7.34(t,J＝7.0Hz,
1H),7.25–7.08(m,5H),6.99(d,J＝8.3Hz,1H),4.40–4.27(m,1H),3.28(br s,2H),1.06(d,J＝6.1Hz,3H),0.95(d,J＝6.1Hz,3H).13C NMR(101MHz,CDCl3)δ154.43,142.13,134.33,
133.96,130.11,129.71,128.93,128.24,128.12,127.96,126.80,126.20,125.43,124.72,-1
124.26,122.10,121.77,119.07,118.30,114.42,72.85,22.57,22.46.ATR-FTIR(cm ):
3473,3382,3055,2974,2927,1620,1505,1381,1240,1111,810,748.ESI-MS:calculated[C23H21NO+H]+:328.1695,found:328.1706.[α]20D＝+51.2(c＝1.28,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝5.7min,t2(minor)＝6.6min.。
1H),7.25–7.08(m,5H),6.99(d,J＝8.3Hz,1H),4.40–4.27(m,1H),3.28(br s,2H),1.06(d,J＝6.1Hz,3H),0.95(d,J＝6.1Hz,3H).13C NMR(101MHz,CDCl3)δ154.43,142.13,134.33,
133.96,130.11,129.71,128.93,128.24,128.12,127.96,126.80,126.20,125.43,124.72,-1
124.26,122.10,121.77,119.07,118.30,114.42,72.85,22.57,22.46.ATR-FTIR(cm ):
3473,3382,3055,2974,2927,1620,1505,1381,1240,1111,810,748.ESI-MS:calculated[C23H21NO+H]+:328.1695,found:328.1706.[α]20D＝+51.2(c＝1.28,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝5.7min,t2(minor)＝6.6min.。
[0046] 实施例7：(R)-2'-苄氧基-[1,1'-联萘]-2-胺的制备(3g)
[0047]
[0048] (R)-2'-苄氧基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3g，制备方法与实施例2相同。
[0049] 产物收率76％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90(d,J＝9.0Hz,1H),7.84(d,J＝8.2Hz,1H),7.78(d,J＝8.5Hz,2H),7.42(d,J＝9.0Hz,1H),7.33(t,J＝7.0Hz,
1H),7.28–7.08(m,8H),7.03–6.95(m,3H),5.05(d,J＝12.5Hz,1H),5.00(d,J＝12.5Hz,
1H),3.29(br s,2H).13C NMR(101MHz,CDCl3)δ154.53,142.21,137.47,134.36,133.81,
129.99,129.90,129.14,128.32,128.16,128.09,127.60,127.12,127.00,126.42,125.31,
124.54,124.32,122.24,120.58,118.33,116.80,113.93,71.49.ATR-FTIR(cm-1):3473,
3381,3056,2925,1620,1506,1272,1220,810,746.ESI-MS:calculated[C27H21NO+H]+:
376.1695,found:376.1700.[α]20D＝+73.4(c＝1.06,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝7.3min,t2(minor)＝
10.8min.。
1H),7.28–7.08(m,8H),7.03–6.95(m,3H),5.05(d,J＝12.5Hz,1H),5.00(d,J＝12.5Hz,
1H),3.29(br s,2H).13C NMR(101MHz,CDCl3)δ154.53,142.21,137.47,134.36,133.81,
129.99,129.90,129.14,128.32,128.16,128.09,127.60,127.12,127.00,126.42,125.31,
124.54,124.32,122.24,120.58,118.33,116.80,113.93,71.49.ATR-FTIR(cm-1):3473,
3381,3056,2925,1620,1506,1272,1220,810,746.ESI-MS:calculated[C27H21NO+H]+:
376.1695,found:376.1700.[α]20D＝+73.4(c＝1.06,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝7.3min,t2(minor)＝
10.8min.。
[0050] 实施例8：(R)-2'-(环己基氧基)-[1,1'-联萘]-2-胺的制备(3h)
[0051]
[0052] (R)-2'-(环己基氧基)-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3h，制备方法与实施例2相同。
[0053] 产物收率89％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90(d,J＝9.0Hz,1H),7.85(d,J＝8.1Hz,1H),7.75(d,J＝8.3Hz,2H),7.41(d,J＝9.0Hz,1H),7.35–7.28(m,1H),
7.23–7.07(m,5H),6.99(d,J＝8.3Hz,1H),4.13–4.03(m,1H),3.34(br s,2H),1.73–1.64(m,1H),1.57–1.44(m,2H),1.36–1.25(m,3H),1.18–0.93(m,4H).13C NMR(101MHz,CDCl3)δ
154.23,142.13,134.37,134.01,129.96,129.61,128.88,128.23,128.09,127.91,126.77,
126.13,125.37,124.76,124.13,122.07,121.44,118.71,118.26,114.52,77.77,32.29,
32.11,25.50,23.59,23.45.ATR-FTIR(cm-1):3473,3382,3055,2932,2855,1620,1505,
1264,1235,811,747.ESI-MS:calculated[C26H25NO+H]+:368.2008,found:368.2017.[α]20D＝+53.7(c＝0.94,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝8.4min,t2(minor)＝9.8min.。
7.23–7.07(m,5H),6.99(d,J＝8.3Hz,1H),4.13–4.03(m,1H),3.34(br s,2H),1.73–1.64(m,1H),1.57–1.44(m,2H),1.36–1.25(m,3H),1.18–0.93(m,4H).13C NMR(101MHz,CDCl3)δ
154.23,142.13,134.37,134.01,129.96,129.61,128.88,128.23,128.09,127.91,126.77,
126.13,125.37,124.76,124.13,122.07,121.44,118.71,118.26,114.52,77.77,32.29,
32.11,25.50,23.59,23.45.ATR-FTIR(cm-1):3473,3382,3055,2932,2855,1620,1505,
1264,1235,811,747.ESI-MS:calculated[C26H25NO+H]+:368.2008,found:368.2017.[α]20D＝+53.7(c＝0.94,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝8.4min,t2(minor)＝9.8min.。
[0054] 实施例9：(R)-2'-(1-丙烯基氧基)-[1,1'-联萘]-2-胺的制备(3i)
[0055]
[0056] (R)-2'-(烯丙氧基)-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3i，制备方法与实施例2相同。
[0057] 产物收率79％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.95(d,J＝9.0Hz,1H),7.89(d,J＝8.2Hz,1H),7.78–7.74(m,2H),7.44(d,J＝8.9Hz,1H),7.38(t,J＝7.0Hz,1H),
7.32–7.25(m,2H),7.23–7.13(m,2H),7.09(d,J＝8.7Hz,1H),7.00(d,J＝8.2Hz,1H),6.29(d,J＝5.9Hz,1H),4.63–4.52(m,1H),3.57(br s,2H),1.26(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ153.38,142.38,141.59,134.35,133.69,130.67,130.07,129.28,
128.28,128.23,128.01,127.16,126.38,125.55,124.76,124.46,122.19,120.71,118.21,
117.69,113.19,107.35,9.12.ATR-FTIR(cm-1):3468,3385,3054,2924,2856,1668,1621,
1246,813,747.ESI-MS:calculated[C23H19NO+H]+:326.1539,found:326.1547.[α]20D＝+
120.2(c＝0.33,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99/1,detector:254nm,flow rate:
1mL/min),t1(major)＝9.4min,t2(minor)＝10.5min.。
7.32–7.25(m,2H),7.23–7.13(m,2H),7.09(d,J＝8.7Hz,1H),7.00(d,J＝8.2Hz,1H),6.29(d,J＝5.9Hz,1H),4.63–4.52(m,1H),3.57(br s,2H),1.26(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ153.38,142.38,141.59,134.35,133.69,130.67,130.07,129.28,
128.28,128.23,128.01,127.16,126.38,125.55,124.76,124.46,122.19,120.71,118.21,
117.69,113.19,107.35,9.12.ATR-FTIR(cm-1):3468,3385,3054,2924,2856,1668,1621,
1246,813,747.ESI-MS:calculated[C23H19NO+H]+:326.1539,found:326.1547.[α]20D＝+
120.2(c＝0.33,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99/1,detector:254nm,flow rate:
1mL/min),t1(major)＝9.4min,t2(minor)＝10.5min.。
[0058] 实施例10：(R)-2'-(甲氧基甲氧基)-[1,1'-联萘]-2-胺的制备(3j)
[0059]
[0060] (R)-2'-(甲氧基甲氧基)-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3j，制备方法与实施例2相同。
[0061] 产物收率86％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.95(d,J＝9.0Hz,1H),7.87(d,J＝8.2Hz,1H),7.79–7.73(m,2H),7.56(d,J＝9.0Hz,1H),7.38–7.33(m,1H),7.26–
7.12(m,4H),7.09(d,J＝8.7Hz,1H),7.00(d,J＝8.2Hz,1H),5.05(d,J＝6.8Hz,1H),4.99(d,J＝6.8Hz,1H),3.30(br s,2H),3.15(s,3H).13C NMR(101MHz,CDCl3)δ153.16,142.16,
134.29,133.65,130.49,129.99,129.16,128.23,128.18,128.05,126.97,126.44,125.35,
124.61,124.42,122.27,121.16,118.26,117.92,113.82,95.30,56.10.ATR-FTIR(cm-1):
3471,3379,3055,2924,1620,1506,1239,1148,1014,813,749.ESI-MS:calculated[C22H19NO2+H]+:330.1488,found:330.1494.[α]20D＝+99.6(c＝1.04,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝7.3min,t2(minor)＝9.1min.。
7.12(m,4H),7.09(d,J＝8.7Hz,1H),7.00(d,J＝8.2Hz,1H),5.05(d,J＝6.8Hz,1H),4.99(d,J＝6.8Hz,1H),3.30(br s,2H),3.15(s,3H).13C NMR(101MHz,CDCl3)δ153.16,142.16,
134.29,133.65,130.49,129.99,129.16,128.23,128.18,128.05,126.97,126.44,125.35,
124.61,124.42,122.27,121.16,118.26,117.92,113.82,95.30,56.10.ATR-FTIR(cm-1):
3471,3379,3055,2924,1620,1506,1239,1148,1014,813,749.ESI-MS:calculated[C22H19NO2+H]+:330.1488,found:330.1494.[α]20D＝+99.6(c＝1.04,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝7.3min,t2(minor)＝9.1min.。
[0062] 实施例11：(R)-6,6'-二溴-2'-乙氧基-[1,1'-联萘]-2-胺的制备(3k)[0063]
[0064] 在空气环境下，在反应管中加入(R)-6,6'-二溴-2'-乙氧基-[1,1'-联萘]-2-醇(0.2mmol),2b(0.3mmol),碳酸钾(0.3mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌12h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失后，将反应管从油浴锅中提起，直接在反应管中加入碳酸铯(2.5mmol),然后放入预先升温至130℃的油浴锅中搅拌3h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3k。
[0065] 产物收率82％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ8.03(s,1H),7.92(s,1H),7.88(d,J＝9.0Hz,1H),7.68(d,J＝8.8Hz,1H),7.46(d,J＝9.0Hz,1H),7.31(d,J＝
9.0Hz,1H),7.21(d,J＝8.9Hz,1H),7.12(d,J＝8.8Hz,1H),7.04(d,J＝9.0Hz,1H),6.81(d,J＝9.0Hz,1H),4.11–4.01(m,2H),3.60(br s,2H),1.10(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ155.09,142.62,132.74,132.20,130.79,130.33,130.17,130.02,129.55,129.34,
129.26,128.30,126.92,126.13,119.45,119.25,118.00,117.06,115.75,113.35,65.34,
15.06.ATR-FTIR(cm-1):3477,3385,2924,3853,1620,1585,1493,1385,1259,1068,
809.ESI-MS:calculated[C22H17NOBr2+H]+:469.9749,found:469.9756.[α]20D＝+99.6(c＝
1.04,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝14.8min,t2(minor)＝23.0min.。
9.0Hz,1H),7.21(d,J＝8.9Hz,1H),7.12(d,J＝8.8Hz,1H),7.04(d,J＝9.0Hz,1H),6.81(d,J＝9.0Hz,1H),4.11–4.01(m,2H),3.60(br s,2H),1.10(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ155.09,142.62,132.74,132.20,130.79,130.33,130.17,130.02,129.55,129.34,
129.26,128.30,126.92,126.13,119.45,119.25,118.00,117.06,115.75,113.35,65.34,
15.06.ATR-FTIR(cm-1):3477,3385,2924,3853,1620,1585,1493,1385,1259,1068,
809.ESI-MS:calculated[C22H17NOBr2+H]+:469.9749,found:469.9756.[α]20D＝+99.6(c＝
1.04,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(major)＝14.8min,t2(minor)＝23.0min.。
[0066] 实施例12：(R)-2'-乙氧基-6,6'-二苯基-[1,1'-联萘]-2-胺的制备(3l)[0067]
[0068] (R)-2'-乙氧基-6,6'-二苯基-[1,1'-联萘]-2-醇和2b作为反应的起始底物制备目标产物3l，制备方法与实施例2相同。
[0069] 产物收率83％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ8.14(s,1H),8.06(d,J＝8.5Hz,2H),7.89(d,J＝8.7Hz,1H),7.71(d,J＝7.6Hz,4H),7.57(d,J＝8.8Hz,1H),7.54–7.43(m,6H),7.41–7.32(m,3H),7.17(t,J＝8.5Hz,2H),4.18–4.06(m,2H),3.66(br s,2H),
1.15(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ155.01,142.42,141.51,141.15,136.85,
134.76,133.60,133.03,130.29,130.07,129.40,128.94,128.84,128.47,127.33,127.25,
127.16,126.83,126.66,126.09,126.07,125.91,125.85,125.08,119.87,118.73,116.85,
113.88,65.48,15.15.ATR-FTIR(cm-1):3474,3382,3058,2925,1621,1593,1492,1387,
1262,1073,758,697.ESI-MS:calculated[C34H27NO+H]+:466.2165,found:466.2168.[α]20D＝-132.7(c＝1.05,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝15.5min,t2(major)＝29.1min.。
1.15(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ155.01,142.42,141.51,141.15,136.85,
134.76,133.60,133.03,130.29,130.07,129.40,128.94,128.84,128.47,127.33,127.25,
127.16,126.83,126.66,126.09,126.07,125.91,125.85,125.08,119.87,118.73,116.85,
113.88,65.48,15.15.ATR-FTIR(cm-1):3474,3382,3058,2925,1621,1593,1492,1387,
1262,1073,758,697.ESI-MS:calculated[C34H27NO+H]+:466.2165,found:466.2168.[α]20D＝-132.7(c＝1.05,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝15.5min,t2(major)＝29.1min.。
[0070] 实施例13：(R)-2'-氨基-3,3'-二甲基-[1,1'-联萘]-2-醇的制备(3m)[0071]
[0072] 在空气环境下，在反应管中加入1(0.2mmol),2b(0.2mmol),碳酸钾(0.2mmol)，碘化钾(0.02mmol)，丙酮(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至70℃的油浴锅中搅拌48h；待反应管冷却至室温，向反应管中加入5ml水，然后用乙酸乙酯萃取旋干，经柱层析分离得到单烷基化反应中间体。将分离出的单烷基化反应中间体转移至另外一个反应管中，以二甲基亚砜(2ml)作为反应溶剂，加入氢氧化钠(2.5mmol),然后放入预先升温至130℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3m。
[0073] 产物收率68％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.80(d,J＝8.1Hz,1H),7.74(d,J＝8.6Hz,3H),7.30(t,J＝7.4Hz,1H),7.25–7.14(m,3H),7.07(d,J＝8.3Hz,1H),
6.98(d,J＝8.3Hz,1H),5.19(br s,1H),3.72(br s,2H),2.51(s,3H),2.43(s,3H).13C NMR(101MHz,CDCl3)δ151.26,143.33,133.09,132.07,130.12,129.79,129.62,128.39,
127.59,127.57,127.06,126.44,126.03,125.20,124.48,123.77,123.67,122.82,114.18,
108.80,18.55,17.18.ATR-FTIR(cm-1):3486,3388,2925,2854,1628,1434,1385,1207,
1098,749.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:314.1542.[α]20D＝+57.6(c＝0.40,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝5.7min,t2(minor)＝6.4min.。
6.98(d,J＝8.3Hz,1H),5.19(br s,1H),3.72(br s,2H),2.51(s,3H),2.43(s,3H).13C NMR(101MHz,CDCl3)δ151.26,143.33,133.09,132.07,130.12,129.79,129.62,128.39,
127.59,127.57,127.06,126.44,126.03,125.20,124.48,123.77,123.67,122.82,114.18,
108.80,18.55,17.18.ATR-FTIR(cm-1):3486,3388,2925,2854,1628,1434,1385,1207,
1098,749.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:314.1542.[α]20D＝+57.6(c＝0.40,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝85/15,detector:254nm,flow rate:1mL/min),t1(major)＝5.7min,t2(minor)＝6.4min.。
[0074] 实施例14：(R)-2'-(甲基氨基)-[1,1'-联萘]-2-醇的制备(3n)
[0075]
[0076] 在空气环境下，在反应管中加入1a(0.2mmol),2ca(0.3mmol),碳酸钾(0.3mmol)，碘化钾(0.02mmol)，丙酮(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h；待反应管冷却至室温，向反应管中加入5ml水，然后用乙酸乙酯萃取旋干，经柱层析分离得到单烷基化反应中间体。将分离出的单烷基化反应中间体转移至另外一个反应管中，以二甲基亚砜(2ml)作为反应溶剂，加入氢氧化钾(2.5mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3n。
[0077] 产物收率62％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.94(t,J＝9.6Hz,2H),7.87(d,J＝8.1Hz,1H),7.80(d,J＝8.4Hz,1H),7.40–7.31(m,2H),7.27–7.17(m,4H),7.13
13
(d,J＝8.3Hz,1H),6.97(d,J＝8.4Hz,1H),5.15(br s,1H),3.68(br s,1H),2.83(s,3H). C NMR(101MHz,CDCl3)δ152.13,146.33,134.18,133.56,130.96,130.49,129.69,128.42,
128.39,127.53,127.35,127.08,124.70,123.78,123.52,122.19,117.80,114.31,113.32,
107.65,30.92.ATR-FTIR(cm-1):3459,3421,2924,2854,1618,1598,1512,1342,1172,815,+ 20
748.ESI-MS:calculated[C21H17NO+H]:300.1382,found:300.1389.[α] D＝+91.2(c＝
0.65,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.9min,t2(major)＝5.9min.。
13
(d,J＝8.3Hz,1H),6.97(d,J＝8.4Hz,1H),5.15(br s,1H),3.68(br s,1H),2.83(s,3H). C NMR(101MHz,CDCl3)δ152.13,146.33,134.18,133.56,130.96,130.49,129.69,128.42,
128.39,127.53,127.35,127.08,124.70,123.78,123.52,122.19,117.80,114.31,113.32,
107.65,30.92.ATR-FTIR(cm-1):3459,3421,2924,2854,1618,1598,1512,1342,1172,815,+ 20
748.ESI-MS:calculated[C21H17NO+H]:300.1382,found:300.1389.[α] D＝+91.2(c＝
0.65,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.9min,t2(major)＝5.9min.。
[0078] 实施例15：(R)-2'-(乙基氨基)-[1,1'-联萘]-2-醇的制备(3o)
[0079]
[0080] 1a和2cb作为反应的起始底物制备目标产物3o，制备方法与实施例14相同。
[0081] 产物收率65％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.96–7.82(m,3H),7.80–7.72(m,1H),7.37(d,J＝8.9Hz,1H),7.32(t,J＝7.4Hz,1H),7.26–7.11(m,5H),6.94(d,J＝7.5Hz,1H),5.17(br s,1H),3.59(br s,1H),3.20(q,J＝6.9Hz,2H),1.02(t,J＝
7.0Hz,3H).13C NMR(101MHz,CDCl3)δ152.09,145.43,134.29,133.52,130.81,130.45,
129.64,128.38,128.31,127.56,127.28,127.03,124.69,123.75,123.58,122.22,117.78,
114.28,114.08,108.07,38.50,15.21.ATR-FTIR(cm-1):3465,3409,3055,2966,2926,1618,
1597,1511,1204,1150,815,748.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:
314.1546.[α]20D＝+115.6(c＝1.0,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝5.0min,t2(major)＝6.1min.。
7.0Hz,3H).13C NMR(101MHz,CDCl3)δ152.09,145.43,134.29,133.52,130.81,130.45,
129.64,128.38,128.31,127.56,127.28,127.03,124.69,123.75,123.58,122.22,117.78,
114.28,114.08,108.07,38.50,15.21.ATR-FTIR(cm-1):3465,3409,3055,2966,2926,1618,
1597,1511,1204,1150,815,748.ESI-MS:calculated[C22H19NO+H]+:314.1539,found:
314.1546.[α]20D＝+115.6(c＝1.0,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝5.0min,t2(major)＝6.1min.。
[0082] 实施例16：(R)-2'-(丙基氨基)-[1,1'-联萘]-2-醇的制备(3p)
[0083]
[0084] 1a和2cc作为反应的起始底物制备目标产物3p，制备方法与实施例14相同。
[0085] 产物收率61％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.95–7.84(m,3H),7.77(d,J＝8.0Hz,1H),7.37(d,J＝8.9Hz,1H),7.32(t,J＝7.4Hz,1H),7.26–7.12(m,5H),6.95(d,J＝7.9Hz,1H),5.16(br s,1H),3.68(br s,1H),3.17–3.04(m,2H),1.44–1.38(m,2H),0.75(t,J＝7.4Hz,3H).13C NMR(101MHz,CDCl3)δ152.12,145.51,134.32,133.54,130.78,
130.46,129.65,128.38,128.32,127.50,127.29,127.03,124.72,123.76,123.53,122.17,
117.76,114.30,114.07,107.87,45.68,22.94,11.32.ATR-FTIR(cm-1):3466,3412,2959,
2928,1618,1597,1511,1427,1343,1203,1149,815,748.ESI-MS:calculated[C23H21NO+H]+:
328.1695,found:328.1700.[α]20D＝+130.0(c＝1.0,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.6min,t2(major)＝
5.8min.。
130.46,129.65,128.38,128.32,127.50,127.29,127.03,124.72,123.76,123.53,122.17,
117.76,114.30,114.07,107.87,45.68,22.94,11.32.ATR-FTIR(cm-1):3466,3412,2959,
2928,1618,1597,1511,1427,1343,1203,1149,815,748.ESI-MS:calculated[C23H21NO+H]+:
328.1695,found:328.1700.[α]20D＝+130.0(c＝1.0,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.6min,t2(major)＝
5.8min.。
[0086] 实施例17：(R)-2'-(丁基氨基)-[1,1'-联萘]-2-醇的制备(3q)
[0087]
[0088] 1a和2cd作为反应的起始底物制备目标产物3q，制备方法与实施例14相同。
[0089] 产物收率55％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.95–7.83(m,3H),7.77(d,J＝8.4Hz,1H),7.37(d,J＝8.9Hz,1H),7.32(t,J＝7.3Hz,1H),7.27–7.11(m,5H),6.95(d,J＝8.0Hz,1H),5.15(br s,1H),3.65(br s,1H),3.21–3.09(m,2H),1.42–1.34(m,2H),1.22–1.12(m,2H),0.79(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ152.13,145.56,
134.32,133.55,130.80,130.46,129.66,128.38,128.32,127.52,127.30,127.01,124.73,
123.75,123.55,122.17,117.75,114.31,114.08,107.88,43.67,31.87,20.05,13.87.ATR--1
FTIR(cm ):3464,3414,2928,2856,1619,1598,1512,1427,1202,1146,815,747.ESI-MS:
calculated[C24H23NO+H]+:342.1852,found:342.1858.[α]20D＝+126.6(c＝0.82,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝6.5min.。
134.32,133.55,130.80,130.46,129.66,128.38,128.32,127.52,127.30,127.01,124.73,
123.75,123.55,122.17,117.75,114.31,114.08,107.88,43.67,31.87,20.05,13.87.ATR--1
FTIR(cm ):3464,3414,2928,2856,1619,1598,1512,1427,1202,1146,815,747.ESI-MS:
calculated[C24H23NO+H]+:342.1852,found:342.1858.[α]20D＝+126.6(c＝0.82,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝6.5min.。
[0090] 实施例18：(R)-2'-(环己基氨基)-[1,1'-联萘]-2-醇的制备(3r)
[0091]
[0092] 在空气环境下，在反应管中加入1a(0.2mmol),2bk(0.6mmol),碳酸钾(0.6mmol)，碘化钾(0.02mmol)，丙酮(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至70℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失后，将反应管从油浴锅中提起，待冷却至室温后用硅藻土抽滤旋干，直接转移至另外一个反应管中以二甲基亚砜(2ml)作为反应溶剂，加入氢氧化钾(2.5mmol),然后放入预先升温至150℃的油浴锅中搅拌10h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3r。
[0093] 产物收率51％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.96–7.84(m,3H),7.77(d,J＝7.3Hz,1H),7.40–7.31(m,2H),7.27–7.12(m,5H),6.92(d,J＝8.2Hz,1H),5.15(br s,1H),3.49(br s,1H),3.44–3.36(m,1H),1.93(d,J＝12.3Hz,1H),1.85(d,J＝12.5Hz,1H),1.66–1.56(m,2H),1.32–1.21(m,3H),1.10–1.01(m,1H),0.99–0.90(m,1H),0.88–0.79(m,1H).13C NMR(101MHz,CDCl3)δ152.05,144.85,134.46,133.56,130.71,130.46,129.64,
128.36,128.27,127.56,127.25,126.99,124.81,123.74,123.62,122.23,117.69,115.10,
114.32,108.30,52.01,33.71,33.64,25.73,24.99.ATR-FTIR(cm-1):3467,3404,2925,+
2853,1619,1597,1427,1343,1262,815,748.ESI-MS:calculated[C26H25NO+H]:368.2008,found:368.2011.[α]20D＝+88.0(c＝0.37,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝5.4min,t2(major)＝11.2min.。
128.36,128.27,127.56,127.25,126.99,124.81,123.74,123.62,122.23,117.69,115.10,
114.32,108.30,52.01,33.71,33.64,25.73,24.99.ATR-FTIR(cm-1):3467,3404,2925,+
2853,1619,1597,1427,1343,1262,815,748.ESI-MS:calculated[C26H25NO+H]:368.2008,found:368.2011.[α]20D＝+88.0(c＝0.37,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝5.4min,t2(major)＝11.2min.。
[0094] 实施例19：(R)-N，2'-二甲基-[1,1'-联萘]-2-胺的制备(3s)
[0095]
[0096] (R)-2'-甲基-[1,1'-联萘]-2-醇和2ba作为反应的起始底物制备目标产物3s，制备方法与实施例2相同。
[0097] 产物收率97％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.92–7.84(m,3H),7.78(d,J＝7.9Hz,1H),7.52(d,J＝8.4Hz,1H),7.42–7.36(m,1H),7.24–7.08(m,5H),6.81(d,J＝8.3Hz,1H),3.35(br s,1H),2.79(s,3H),2.09(s,3H).13C NMR(101MHz,CDCl3)δ144.45,136.44,133.52,133.15,132.79,132.19,129.26,129.18,128.17,128.13,128.09,127.39,
126.51,125.69,125.32,123.83,121.71,115.79,113.35,31.24,20.13.ATR-FTIR(cm-1):
3423,3053,2923,1618,1598,1495,1470,1341,811,745.ESI-MS:calculated[C22H19N+H]+:
20
298.1590,found:298.1597.[α] D＝+45.0(c＝1.08,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.76/0.24,detector:254nm,flow rate:1mL/min),t1(minor)＝19.2min,t2(major)＝
21.3min.。
126.51,125.69,125.32,123.83,121.71,115.79,113.35,31.24,20.13.ATR-FTIR(cm-1):
3423,3053,2923,1618,1598,1495,1470,1341,811,745.ESI-MS:calculated[C22H19N+H]+:
20
298.1590,found:298.1597.[α] D＝+45.0(c＝1.08,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.76/0.24,detector:254nm,flow rate:1mL/min),t1(minor)＝19.2min,t2(major)＝
21.3min.。
[0098] 实施例20：(R)-N-乙基-2'-甲基-[1,1'-联萘]-2-胺的制备(3t)
[0099]
[0100] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bb作为反应的起始底物制备目标产物3t，制备方法与实施例2相同。
[0101] 产物收率86％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.84(m,3H),7.77(d,J＝7.9Hz,1H),7.53(d,J＝8.4Hz,1H),7.42–7.36(m,1H),7.26–7.19(m,3H),7.16(t,J＝7.3Hz,1H),7.10(t,J＝7.4Hz,1H),6.79(d,J＝8.3Hz,1H),3.29(br s,1H),3.23–3.15(m,2H),2.10(s,3H),0.99(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ143.33,136.40,133.69,133.14,132.77,132.11,129.23,129.11,128.12,127.55,126.49,125.73,125.33,-1
123.95,121.86,116.43,114.27,38.89,20.11,15.39.ATR-FTIR(cm ):3406,3053,2924,
2854,1619,1598,1510,1425,1337,1152,811,745.ESI-MS:calculated[C23H21N+H]+:
312.1746,found:312.1752.[α]20D＝+67.2(c＝0.51,CH2Cl2).HPLC:99％ee(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.1min,t2(major)＝17.8min.。
123.95,121.86,116.43,114.27,38.89,20.11,15.39.ATR-FTIR(cm ):3406,3053,2924,
2854,1619,1598,1510,1425,1337,1152,811,745.ESI-MS:calculated[C23H21N+H]+:
312.1746,found:312.1752.[α]20D＝+67.2(c＝0.51,CH2Cl2).HPLC:99％ee(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.1min,t2(major)＝17.8min.。
[0102] 实施例21：(R)-N-丙基-2'-甲基-[1,1'-联萘]-2-胺的制备(3u)
[0103]
[0104] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bc作为反应的起始底物制备目标产物3u，制备方法与实施例2相同。
[0105] 产物收率88％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.87(t,J＝8.3Hz,3H),7.77(d,J＝7.9Hz,1H),7.53(d,J＝8.4Hz,1H),7.42–7.36(m,1H),7.27–7.20(m,3H),7.18–
7.07(m,2H),6.79(d,J＝8.3Hz,1H),3.39(br s,1H),3.15–3.06(m,2H),2.10(s,3H),1.43–
13
1.34(m,2H),0.71(t,J＝7.4Hz,3H). C NMR(101MHz,CDCl3)δ143.56,136.42,133.72,
133.15,132.77,132.20,129.22,129.05,128.12,128.09,127.37,126.47,125.78,125.32,
123.87,121.69,115.98,114.11,46.03,23.12,20.12,11.38.ATR-FTIR(cm-1):3412,3053,
2959,2924,1619,1598,1511,1426,1341,1151,811,745.ESI-MS:calculated[C24H23N+H]+:
326.1903,found:326.1908.[α]20D＝+71.7(c＝0.90,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝11.4min,t2(major)＝
16.3min.。
7.07(m,2H),6.79(d,J＝8.3Hz,1H),3.39(br s,1H),3.15–3.06(m,2H),2.10(s,3H),1.43–
13
1.34(m,2H),0.71(t,J＝7.4Hz,3H). C NMR(101MHz,CDCl3)δ143.56,136.42,133.72,
133.15,132.77,132.20,129.22,129.05,128.12,128.09,127.37,126.47,125.78,125.32,
123.87,121.69,115.98,114.11,46.03,23.12,20.12,11.38.ATR-FTIR(cm-1):3412,3053,
2959,2924,1619,1598,1511,1426,1341,1151,811,745.ESI-MS:calculated[C24H23N+H]+:
326.1903,found:326.1908.[α]20D＝+71.7(c＝0.90,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝11.4min,t2(major)＝
16.3min.。
[0106] 实施例22：(R)-N-丁基-2'-甲基-[1,1'-联萘]-2-胺的制备(3v)
[0107]
[0108] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bd作为反应的起始底物制备目标产物3v，制备方法与实施例2相同。
[0109] 产物收率87％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.84(m,3H),7.77(d,J＝7.7Hz,1H),7.53(d,J＝8.4Hz,1H),7.42–7.36(m,1H),7.24(d,J＝9.0Hz,1H),7.22(d,J＝3.5Hz,2H),7.18–7.08(m,2H),6.79(d,J＝8.3Hz,1H),3.36(br s,1H),3.19–3.11(m,2H),2.10(s,3H),1.38–1.31(m,2H),1.17–1.07(m,2H),0.77(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ143.59,136.41,133.71,133.15,132.76,132.19,129.21,129.05,128.12,128.09,127.37,126.47,126.45,125.77,125.31,123.87,121.70,116.02,114.12,
43.96,32.06,20.12,20.08,13.89.ATR-FTIR(cm-1):3412,3053,2956,2926,2856,1619,
1598,1512,1493,1426,1340,1295,1151,811,745.ESI-MS:calculated[C25H25N+H]+:
340.2059,found:340.2065.[α]20D＝+79.2(c＝1.06,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.6min,t2(major)＝
17.4min.。
43.96,32.06,20.12,20.08,13.89.ATR-FTIR(cm-1):3412,3053,2956,2926,2856,1619,
1598,1512,1493,1426,1340,1295,1151,811,745.ESI-MS:calculated[C25H25N+H]+:
340.2059,found:340.2065.[α]20D＝+79.2(c＝1.06,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.6min,t2(major)＝
17.4min.。
[0110] 实施例23：(R)-N-十二烷基-2'-甲基-[1,1'-联萘]-2-胺的制备(3w)
[0111]
[0112] (R)-2'-甲基-[1,1'-联萘]-2-醇和2be作为反应的起始底物制备目标产物3w，制备方法与实施例2相同。
[0113] 产物收率83％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.84(m,3H),7.77(d,J＝7.8Hz,1H),7.53(d,J＝8.4Hz,1H),7.42–7.37(m,1H),7.25(d,J＝8.9Hz,1H),7.22(d,J＝4.1Hz,2H),7.18–7.08(m,2H),6.80(d,J＝8.3Hz,1H),3.40(br s,1H),3.16–3.08(m,2H),2.10(s,3H),1.39–1.32(m,2H),1.29–1.06(m,18H),0.88(t,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ143.43,136.44,133.69,133.14,132.77,132.13,129.21,129.08,128.13,128.10,127.46,126.50,126.48,125.76,125.33,123.91,121.78,116.20,114.23,
44.36,32.07,29.85,29.78,29.76,29.66,29.64,29.50,29.40,26.90,22.84,20.15,
14.28.ATR-FTIR(cm-1):3414,3054,2924,2853,1619,1598,1513,1426,1341,1150,810,+ 20
744.ESI-MS:calculated[C33H41N+H]:452.3311,found:452.3320.[α] D＝+63.4(c＝0.71,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.5min,t2(major)＝18.5min.。
44.36,32.07,29.85,29.78,29.76,29.66,29.64,29.50,29.40,26.90,22.84,20.15,
14.28.ATR-FTIR(cm-1):3414,3054,2924,2853,1619,1598,1513,1426,1341,1150,810,+ 20
744.ESI-MS:calculated[C33H41N+H]:452.3311,found:452.3320.[α] D＝+63.4(c＝0.71,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝12.5min,t2(major)＝18.5min.。
[0114] 实施例24：(R)-N-十六烷基-2'-甲基-[1,1'-联萘]-2-胺的制备(3x)
[0115]
[0116] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bf作为反应的起始底物制备目标产物3x，制备方法与实施例2相同。
[0117] 产物收率77％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.84(m,3H),7.77(d,J＝7.7Hz,1H),7.53(d,J＝8.4Hz,1H),7.42–7.37(m,1H),7.25(d,J＝8.9Hz,1H),7.21(d,J＝4.2Hz,2H),7.19–7.08(m,2H),6.80(d,J＝8.3Hz,1H),3.40(br s,1H),3.17–3.09(m,2H),2.10(s,3H),1.36–1.08(m,28H),0.88(t,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ143.41,136.44,133.69,133.14,132.77,132.12,129.21,129.09,128.13,128.11,127.48,
126.50,126.49,125.76,125.34,123.91,121.80,116.25,114.25,44.39,32.08,29.85,
29.85,29.82,29.78,29.66,29.64,29.52,29.40,26.90,22.85,20.15,14.28.ATR-FTIR(cm-1):3413,3054,2924,2853,1619,1598,1513,1426,1341,1298,1150,810,744.ESI-MS:
+ 20
calculated[C37H49N+H] :508.3937,found:508.3938.[α] D＝+54.6(c＝0.75,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝13.4min,t2(major)＝17.7min.。
126.50,126.49,125.76,125.34,123.91,121.80,116.25,114.25,44.39,32.08,29.85,
29.85,29.82,29.78,29.66,29.64,29.52,29.40,26.90,22.85,20.15,14.28.ATR-FTIR(cm-1):3413,3054,2924,2853,1619,1598,1513,1426,1341,1298,1150,810,744.ESI-MS:
+ 20
calculated[C37H49N+H] :508.3937,found:508.3938.[α] D＝+54.6(c＝0.75,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝13.4min,t2(major)＝17.7min.。
[0118] 实施例25：(R)-N-(3-甲氧基丙基)-2'-甲基-[1,1'-联萘]-2-胺的制备(3y)[0119]
[0120] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bg作为反应的起始底物制备目标产物3y，制备方法与实施例2相同。
[0121] 产物收率87％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.89–7.84(m,3H),7.77(d,J＝7.9Hz,1H),7.53(d,J＝8.4Hz,1H),7.41–7.35(m,1H),7.25(d,J＝8.9Hz,1H),7.21(d,J＝4.1Hz,2H),7.18–7.07(m,2H),6.79(d,J＝8.3Hz,1H),3.66(br s,1H),3.30–3.11(m,4H),2.96(s,3H),2.10(s,3H),1.69–1.61(m,2H).13C NMR(101MHz,CDCl3)δ143.62,136.43,133.72,133.19,132.80,132.28,129.22,129.08,128.11,128.09,128.03,127.36,
126.46,126.41,125.79,125.26,123.88,121.66,116.00,113.87,70.76,58.47,41.82,
29.66,20.12.ATR-FTIR(cm-1):3373,3053,2922,1618,1598,1507,1426,1339,1118,812,
746.ESI-MS:calculated[C25H25NO+H]+:356.2008,found:356.2016.[α]20D＝+97.3(c＝
0.90,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:0.7mL/min),t1(minor)＝10.8min,t2(major)＝12.9min.。
126.46,126.41,125.79,125.26,123.88,121.66,116.00,113.87,70.76,58.47,41.82,
29.66,20.12.ATR-FTIR(cm-1):3373,3053,2922,1618,1598,1507,1426,1339,1118,812,
746.ESI-MS:calculated[C25H25NO+H]+:356.2008,found:356.2016.[α]20D＝+97.3(c＝
0.90,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:0.7mL/min),t1(minor)＝10.8min,t2(major)＝12.9min.。
[0122] 实施例26：(R)-N-(3-甲氧基丙基)-2'-甲基-[1,1'-联萘]-2-胺的制备(3z)[0123]
[0124] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bh作为反应的起始底物制备目标产物3z，制备方法与实施例2相同。
[0125] 产物收率69％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90–7.84(m,3H),7.77(d,J＝7.7Hz,1H),7.54(d,J＝8.4Hz,1H),7.42–7.37(m,1H),7.26–7.20(m,3H),7.18–7.08(m,2H),6.81(d,J＝8.3Hz,1H),3.51(br s,1H),2.99–2.90(m,2H),2.11(s,3H),1.72–1.62(m,1H),0.68(t,J＝6.7Hz,6H).13C NMR(101MHz,CDCl3)δ143.40,136.47,133.72,133.14,132.77,132.14,129.21,129.05,128.14,128.10,127.36,126.51,126.47,125.82,125.35,
123.86,121.71,115.89,114.07,52.08,28.33,20.25,20.23,20.16.ATR-FTIR(cm-1):3419,
3053,2955,2925,1619,1598,1512,1426,1337,1152,810,744.ESI-MS:calculated[C25H25N+ 20
+H]:340.2059,found:340.2064.[α] D＝+86.5(c＝0.55,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝10.7min,t2(major)＝14.4min.。
123.86,121.71,115.89,114.07,52.08,28.33,20.25,20.23,20.16.ATR-FTIR(cm-1):3419,
3053,2955,2925,1619,1598,1512,1426,1337,1152,810,744.ESI-MS:calculated[C25H25N+ 20
+H]:340.2059,found:340.2064.[α] D＝+86.5(c＝0.55,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝10.7min,t2(major)＝14.4min.。
[0126] 实施例27：(R)-2'-甲基-N-苯基-[1,1'-联萘]-2-胺的制备(3aa)
[0127]
[0128] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bi作为反应的起始底物制备目标产物3aa，制备方法与实施例2相同。
[0129] 产物收率39％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.89(d,J＝8.4Hz,2H),7.84(t,J＝9.2Hz,2H),7.68(d,J＝8.9Hz,1H),7.52(d,J＝8.4Hz,1H),7.41(t,J＝7.1Hz,
1H),7.30–7.14(m,6H),6.97(d,J＝8.1Hz,2H),6.93–6.84(m,2H),5.26(br s,1H),2.14(s,
3H).13C NMR(101MHz,CDCl3)δ143.02,139.10,136.25,133.85,133.14,132.70,131.78,
129.34,129.25,128.64,128.35,128.25,128.16,126.72,126.69,125.57,125.44,124.70,
123.35,121.86,120.85,119.47,118.17,20.33.ATR-FTIR(cm-1):3400,3052,2923,2853,
1620,1595,1498,1417,1345,1304,1027,812,742.ESI-MS:calculated[C27H21N+H]+:
360.1746,found:360.1745.[α]20D＝+206.3(c＝0.47,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝16.7min,t2(major)＝
20.1min.。
1H),7.30–7.14(m,6H),6.97(d,J＝8.1Hz,2H),6.93–6.84(m,2H),5.26(br s,1H),2.14(s,
3H).13C NMR(101MHz,CDCl3)δ143.02,139.10,136.25,133.85,133.14,132.70,131.78,
129.34,129.25,128.64,128.35,128.25,128.16,126.72,126.69,125.57,125.44,124.70,
123.35,121.86,120.85,119.47,118.17,20.33.ATR-FTIR(cm-1):3400,3052,2923,2853,
1620,1595,1498,1417,1345,1304,1027,812,742.ESI-MS:calculated[C27H21N+H]+:
360.1746,found:360.1745.[α]20D＝+206.3(c＝0.47,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(minor)＝16.7min,t2(major)＝
20.1min.。
[0130] 实施例28：(R)-N-苄基-2'-甲基-[1,1'-联萘]-2-胺的制备(3ab)
[0131]
[0132] (R)-2'-甲基-[1,1'-联萘]-2-醇和2bj作为反应的起始底物制备目标产物3ab，制备方法与实施例2相同。
[0133] 产物收率64％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.88(d,J＝8.4Hz,2H),7.79(d,J＝9.0Hz,1H),7.75(d,J＝7.8Hz,1H),7.54(d,J＝8.4Hz,1H),7.44–7.38(m,1H),
7.25(d,J＝3.6Hz,2H),7.22–7.09(m,8H),6.82(d,J＝8.2Hz,1H),4.40–4.30(m,2H),3.90(br s,1H),2.13(s,3H).13C NMR(101MHz,CDCl3)δ143.09,140.01,136.55,133.65,133.11,
132.82,132.06,129.28,129.07,128.58,128.22,128.18,128.13,127.53,127.04,126.91,
126.54,126.50,125.85,125.39,123.93,121.90,116.18,114.14,47.88,20.21.ATR-FTIR-1
(cm ):3425,3054,2924,2854,1619,1598,1512,1494,1454,1426,1340,1295,1150,811,
743,697.ESI-MS:calculated[C28H23N+H]+:374.1903,found:374.1909.[α]20D＝+66.2(c＝
1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(major)＝18.5min,t2(minor)＝23.4min.。
7.25(d,J＝3.6Hz,2H),7.22–7.09(m,8H),6.82(d,J＝8.2Hz,1H),4.40–4.30(m,2H),3.90(br s,1H),2.13(s,3H).13C NMR(101MHz,CDCl3)δ143.09,140.01,136.55,133.65,133.11,
132.82,132.06,129.28,129.07,128.58,128.22,128.18,128.13,127.53,127.04,126.91,
126.54,126.50,125.85,125.39,123.93,121.90,116.18,114.14,47.88,20.21.ATR-FTIR-1
(cm ):3425,3054,2924,2854,1619,1598,1512,1494,1454,1426,1340,1295,1150,811,
743,697.ESI-MS:calculated[C28H23N+H]+:374.1903,found:374.1909.[α]20D＝+66.2(c＝
1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99.4/0.6,detector:254nm,flow rate:1mL/min),t1(major)＝18.5min,t2(minor)＝23.4min.。
[0134] 实施例29：(R)-N-甲基-2'-苯基-[1,1'-联萘]-2-胺的制备(3ac)
[0135]
[0136] (R)-2'-苯基-[1,1'-联萘]-2-醇和2ba作为反应的起始底物制备目标产物3ac，制备方法与实施例2相同。
[0137] 产物收率88％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.5Hz,1H),7.99(d,J＝8.2Hz,1H),7.80(d,J＝8.9Hz,1H),7.75–7.70(m,2H),7.54–7.48(m,1H),7.38–
7.28(m,2H),7.19–7.12(m,4H),7.09–7.02(m,4H),6.99–6.95(m,1H),3.50(br s,1H),2.69(s,3H).13C NMR(101MHz,CDCl3)δ145.08,141.43,140.76,134.38,133.50,133.16,131.81,
129.28,128.78,128.74,128.62,128.19,128.05,127.48,127.05,126.93,126.75,126.61,-1
126.38,126.25,124.36,121.54,115.85,113.28,31.23.ATR-FTIR(cm ):3423,3054,2922,
1618,1599,1494,1421,1342,1298,1152,811,763,746,700.ESI-MS:calculated[C27H21N+H]+:360.1746,found:360.1757.[α]20D＝-27.9(c＝0.91,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98.8/1.2,detector:254nm,flow rate:1mL/min),t1(major)＝15.5min,t2(minor)＝17.6min.。
7.28(m,2H),7.19–7.12(m,4H),7.09–7.02(m,4H),6.99–6.95(m,1H),3.50(br s,1H),2.69(s,3H).13C NMR(101MHz,CDCl3)δ145.08,141.43,140.76,134.38,133.50,133.16,131.81,
129.28,128.78,128.74,128.62,128.19,128.05,127.48,127.05,126.93,126.75,126.61,-1
126.38,126.25,124.36,121.54,115.85,113.28,31.23.ATR-FTIR(cm ):3423,3054,2922,
1618,1599,1494,1421,1342,1298,1152,811,763,746,700.ESI-MS:calculated[C27H21N+H]+:360.1746,found:360.1757.[α]20D＝-27.9(c＝0.91,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98.8/1.2,detector:254nm,flow rate:1mL/min),t1(major)＝15.5min,t2(minor)＝17.6min.。
[0138] 实施例30：(R)-2'-乙氧基-N-甲基-[1,1'-联萘]-2-胺的制备(3ad)
[0139]
[0140] (R)-2'-乙氧基-[1,1'-联萘]-2-醇和2ba作为反应的起始底物制备目标产物3ad，制备方法与实施例2相同。
[0141] 产物收率88％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.94(d,J＝9.0Hz,1H),7.86(t,J＝8.5Hz,2H),7.76(d,J＝7.8Hz,1H),7.42(d,J＝9.0Hz,1H),7.32(t,J＝7.2Hz,
1H),7.24–7.08(m,5H),6.91(d,J＝8.2Hz,1H),4.06–3.94(m,2H),3.48(br s,1H),2.81(s,
13
3H),1.03(t,J＝7.0Hz,3H). C NMR(101MHz,CDCl3)δ155.08,145.11,134.11,134.04,
129.91,129.13,128.12,128.06,127.42,126.90,126.13,125.30,124.28,124.14,121.53,
120.13,116.68,113.58,113.48,65.48,31.47,15.12.ATR-FTIR(cm-1):3424,3054,2978,
2924,1618,1598,1507,1421,1341,1235,1150,808,747.ESI-MS:calculated[C23H21NO+H]+:
328.1695,found:328.1700.[α]20D＝+106.6(c＝0.98,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:0.7mL/min),t1(minor)＝13.2min,t2(major)＝
19.3min.。
1H),7.24–7.08(m,5H),6.91(d,J＝8.2Hz,1H),4.06–3.94(m,2H),3.48(br s,1H),2.81(s,
13
3H),1.03(t,J＝7.0Hz,3H). C NMR(101MHz,CDCl3)δ155.08,145.11,134.11,134.04,
129.91,129.13,128.12,128.06,127.42,126.90,126.13,125.30,124.28,124.14,121.53,
120.13,116.68,113.58,113.48,65.48,31.47,15.12.ATR-FTIR(cm-1):3424,3054,2978,
2924,1618,1598,1507,1421,1341,1235,1150,808,747.ESI-MS:calculated[C23H21NO+H]+:
328.1695,found:328.1700.[α]20D＝+106.6(c＝0.98,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:0.7mL/min),t1(minor)＝13.2min,t2(major)＝
19.3min.。
[0142] 实施例31：(R)-7'-氨基-2,2'，3,3'-四氢-1,1'-螺双[茚]-7-醇的制备(3ae)[0143]
[0144] 在空气环境下，在反应管中加入1(R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二醇(0.2mmol),2c(0.3mmol),碳酸钾(0.3mmol)，碘化钾(0.02mmol)，丙酮(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h；待反应管冷却至室温，向反应管中加入5ml水，然后用乙酸乙酯萃取旋干，经柱层析分离得到单烷基化反应中间体。将分离出的单烷基化反应中间体转移至另外一个反应管中，以二甲基亚砜(2ml)作为反应溶剂，加入氢氧化钾(2.5mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3ae。
[0145] 产物收率41％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.15(t,J＝7.7Hz,1H),7.08(t,J＝7.7Hz,1H),6.87(d,J＝7.4Hz,1H),6.73(d,J＝7.4Hz,1H),6.67(d,J＝8.0Hz,
1H),6.47(d,J＝7.9Hz,1H),4.77(br s,1H),3.45(br s,2H),3.09–2.91(m,4H),2.33–2.08(m,4H).13C NMR(101MHz,CDCl3)δ153.12,145.89,145.39,143.49,131.59,129.66,129.49,
127.81,117.64,115.51,114.02,113.89,58.13,37.56,35.46,31.31,31.22.ATR-FTIR(cm-1):3054,3375,2926,2854,1616,1588,1464,1301,778,745.ESI-MS:calculated[C17H17NO+H]+:252.1382,found:252.1386.[α]20D＝+52.9(c＝0.42,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(minor)＝16.9min,t2(major)＝
20.1min.。
1H),6.47(d,J＝7.9Hz,1H),4.77(br s,1H),3.45(br s,2H),3.09–2.91(m,4H),2.33–2.08(m,4H).13C NMR(101MHz,CDCl3)δ153.12,145.89,145.39,143.49,131.59,129.66,129.49,
127.81,117.64,115.51,114.02,113.89,58.13,37.56,35.46,31.31,31.22.ATR-FTIR(cm-1):3054,3375,2926,2854,1616,1588,1464,1301,778,745.ESI-MS:calculated[C17H17NO+H]+:252.1382,found:252.1386.[α]20D＝+52.9(c＝0.42,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:1mL/min),t1(minor)＝16.9min,t2(major)＝
20.1min.。
[0146] 实施例32：(R)-7'-(甲基氨基)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7-醇的制备(3af)
[0147]
[0148] (R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二醇和2ca作为反应的起始底物制备目标产物3af，制备方法与实施例31相同。
[0149] 产物收率68％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.20(t,J＝7.7Hz,1H),7.16(t,J＝7.7Hz,1H),6.88(d,J＝7.4Hz,1H),6.70(d,J＝7.4Hz,1H),6.67(d,J＝8.0Hz,
1H),6.48(d,J＝8.1Hz,1H),4.79(br s,1H),3.43(br s,1H),3.10–2.92(m,4H),2.68(s,
3H),2.33–2.06(m,4H).13C NMR(101MHz,CDCl3)δ153.16,146.35,145.47,145.20,131.55,
129.93,129.47,126.80,117.59,114.06,113.80,108.30,58.15,37.63,35.07,31.24,
31.23,30.75.ATR-FTIR(cm-1):3500,3423,2930,2855,1589,1475,1313,1239,774,
742.ESI-MS:calculated[C18H19NO+H]+:266.1539,found:266.1545.[α]20D＝+89.4(c＝
0.99,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝5.3min,t2(major)＝6.8min.。
1H),6.48(d,J＝8.1Hz,1H),4.79(br s,1H),3.43(br s,1H),3.10–2.92(m,4H),2.68(s,
3H),2.33–2.06(m,4H).13C NMR(101MHz,CDCl3)δ153.16,146.35,145.47,145.20,131.55,
129.93,129.47,126.80,117.59,114.06,113.80,108.30,58.15,37.63,35.07,31.24,
31.23,30.75.ATR-FTIR(cm-1):3500,3423,2930,2855,1589,1475,1313,1239,774,
742.ESI-MS:calculated[C18H19NO+H]+:266.1539,found:266.1545.[α]20D＝+89.4(c＝
0.99,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝5.3min,t2(major)＝6.8min.。
[0150] 实施例33：(R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯胺的制备(3ag)
[0151]
[0152] (R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯酚和2b作为反应的起始底物制备目标产物3ag，制备方法与实施例2相同。
[0153] 产物收率62％；无色液体；99％ee；1H NMR(400MHz,CDCl3)δ7.68(d,J＝7.9Hz,1H),7.20(t,J＝7.7Hz,1H),6.70(d,J＝8.2Hz,1H),6.65(t,J＝7.5Hz,1H),6.13(br s,2H),
4.32(t,J＝8.6Hz,1H),4.11(dd,J＝16.4,7.6Hz,1H),4.01(t,J＝7.9Hz,1H),1.79(dq,J＝
13.3,6.8Hz,1H),1.03(d,J＝6.7Hz,3H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ
163.63,148.71,132.00,129.68,116.09,115.74,109.32,73.05,68.86,33.34,19.11,
18.74.ATR-FTIR(cm-1):3468,3400,3286,2956,2927,1638,1608,1492,1456,1309,1256,+ 20
1162,1047,748.ESI-MS:calculated[C12H16N2O+H]:205.1335,found:205.1341.[α] D＝+
0.8(c＝1.01,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:
1mL/min),t1(major)＝6.6min,t2(minor)＝7.0min.。
4.32(t,J＝8.6Hz,1H),4.11(dd,J＝16.4,7.6Hz,1H),4.01(t,J＝7.9Hz,1H),1.79(dq,J＝
13.3,6.8Hz,1H),1.03(d,J＝6.7Hz,3H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ
163.63,148.71,132.00,129.68,116.09,115.74,109.32,73.05,68.86,33.34,19.11,
18.74.ATR-FTIR(cm-1):3468,3400,3286,2956,2927,1638,1608,1492,1456,1309,1256,+ 20
1162,1047,748.ESI-MS:calculated[C12H16N2O+H]:205.1335,found:205.1341.[α] D＝+
0.8(c＝1.01,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:
1mL/min),t1(major)＝6.6min,t2(minor)＝7.0min.。
[0154] 实施例34：(R)-2-(4-异丙基-4,5-二氢恶唑-2-基)-N-甲基苯胺的制备(3ah)[0155]
[0156] (R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯酚和2ba作为反应的起始底物制备目标产物3ah，制备方法与实施例2相同。
[0157] 产物收率95％；无色液体；99％ee；1H NMR(400MHz,CDCl3)δ8.39(br s,1H),7.73(d,J＝7.8Hz,1H),7.33(t,J＝7.8Hz,1H),6.68(d,J＝8.4Hz,1H),6.62(t,J＝7.5Hz,1H),4.30(t,J＝8.7Hz,1H),4.11(dd,J＝15.6,8.2Hz,1H),4.00(t,J＝7.9Hz,1H),2.95(d,J＝
5.0Hz,3H),1.80(dq,J＝13.4,6.7Hz,1H),1.04(d,J＝6.7Hz,3H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.95,150.14,132.50,129.88,114.21,109.83,108.57,73.00,
68.58,33.31,29.68,19.18,18.63.ATR-FTIR(cm-1):3265,2958,2819,1635,1589,1528,
1468,1275,1172,1046,971,748.ESI-MS:calculated[C13H18N2O+H]+:219.1491,found:
219.1497.[α]20D＝+21.9(c＝1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:
254nm,flow rate:0.5mL/min),t1(minor)＝7.6min,t2(major)＝9.1min.。
5.0Hz,3H),1.80(dq,J＝13.4,6.7Hz,1H),1.04(d,J＝6.7Hz,3H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.95,150.14,132.50,129.88,114.21,109.83,108.57,73.00,
68.58,33.31,29.68,19.18,18.63.ATR-FTIR(cm-1):3265,2958,2819,1635,1589,1528,
1468,1275,1172,1046,971,748.ESI-MS:calculated[C13H18N2O+H]+:219.1491,found:
219.1497.[α]20D＝+21.9(c＝1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:
254nm,flow rate:0.5mL/min),t1(minor)＝7.6min,t2(major)＝9.1min.。
[0158] 实施例35：(R)-N-乙基-2-(4-异丙基-4,5-二氢恶唑-2-基)苯胺的制备(3ai)[0159]
[0160] (R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯酚和2bb作为反应的起始底物制备目标产物3ai，制备方法与实施例2相同。
[0161] 产物收率83％；无色液体；99％ee；1H NMR(400MHz,CDCl3)δ8.45(br s,1H),7.72(d,J＝7.9Hz,1H),7.29(t,J＝7.7Hz,1H),6.68(d,J＝8.4Hz,1H),6.60(t,J＝7.4Hz,1H),4.32(t,J＝8.6Hz,1H),4.09(dd,J＝16.2,8.0Hz,1H),3.98(t,J＝8.0Hz,1H),3.30–3.21(m,2H),1.81–1.69(m,1H),1.35(t,J＝7.2Hz,3H),1.05(d,J＝6.7Hz,3H),0.96(d,J＝
6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.93,149.29,132.45,129.90,114.12,110.30,
108.36,73.11,68.94,37.58,33.59,19.09,19.02,14.68.ATR-FTIR(cm-1):3254,2962,
2927,2872,1635,1589,1527,1462,1273,1243,1166,1116,1048,971,747.ESI-MS:
calculated[C14H20N2O+H]+:233.1648,found:233.1655.[α]20D＝+9.7(c＝1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝3.8min,t2(major)＝4.1min.。
6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.93,149.29,132.45,129.90,114.12,110.30,
108.36,73.11,68.94,37.58,33.59,19.09,19.02,14.68.ATR-FTIR(cm-1):3254,2962,
2927,2872,1635,1589,1527,1462,1273,1243,1166,1116,1048,971,747.ESI-MS:
calculated[C14H20N2O+H]+:233.1648,found:233.1655.[α]20D＝+9.7(c＝1.0,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝3.8min,t2(major)＝4.1min.。
[0162] 实施例36：(R)-2-(4-异丙基-4,5-二氢恶唑-2-基)-N-丙基苯胺的制备(3aj)[0163]
[0164] (R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯酚和2bc作为反应的起始底物制备目标产物3aj，制备方法与实施例2相同。
[0165] 产物收率73％；无色液体；99％ee；1H NMR(400MHz,CDCl3)δ8.53(br s,1H),7.70(d,J＝7.9Hz,1H),7.27(t,J＝7.8Hz,1H),6.66(d,J＝8.4Hz,1H),6.57(t,J＝7.5Hz,1H),4.30(t,J＝8.7Hz,1H),4.08(dd,J＝16.2,8.0Hz,1H),3.96(t,J＝8.0Hz,1H),3.18(q,J＝
6.4Hz,2H),1.80–1.67(m,3H),1.07–1.01(m,6H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.97,149.40,132.43,129.92,114.01,110.29,108.39,73.10,68.88,44.88,
33.53,22.56,19.03,19.01,11.99.ATR-FTIR(cm-1):3255,2960,2928,2873,1635,1590,
1527,1463,1274,1237,1163,1048,970,746.ESI-MS:calculated[C15H22N2O+H]+:247.1804,found:247.1809.[α]20D＝+9.0(c＝0.89,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:1mL/min),t1(minor)＝3.9min,t2(major)＝4.9min.。
6.4Hz,2H),1.80–1.67(m,3H),1.07–1.01(m,6H),0.94(d,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.97,149.40,132.43,129.92,114.01,110.29,108.39,73.10,68.88,44.88,
33.53,22.56,19.03,19.01,11.99.ATR-FTIR(cm-1):3255,2960,2928,2873,1635,1590,
1527,1463,1274,1237,1163,1048,970,746.ESI-MS:calculated[C15H22N2O+H]+:247.1804,found:247.1809.[α]20D＝+9.0(c＝0.89,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:1mL/min),t1(minor)＝3.9min,t2(major)＝4.9min.。
[0166] 实施例37：(R)-N-丁基-2-(4-异丙基-4,5-二氢恶唑-2-基)苯胺的制备(3ak)[0167]
[0168] (R)-2-(4-异丙基-4,5-二氢恶唑-2-基)苯酚和2bd作为反应的起始底物制备目标产物3ak，制备方法与实施例2相同。
[0169] 产物收率79％；无色液体；99％ee；1H NMR(400MHz,CDCl3)δ8.51(br s,1H),7.70(d,J＝7.8Hz,1H),7.28(t,J＝7.8Hz,1H),6.66(d,J＝8.4Hz,1H),6.57(t,J＝7.5Hz,1H),4.30(t,J＝8.7Hz,1H),4.08(dd,J＝16.2,8.1Hz,1H),3.96(t,J＝8.0Hz,1H),3.20(q,J＝
6.4Hz,2H),1.78–1.63(m,3H),1.55–1.44(m,2H),1.03(d,J＝6.7Hz,3H),0.99–0.92(m,
6H).13C NMR(101MHz,CDCl3)δ163.97,149.41,132.43,129.91,113.98,110.27,108.37,
73.10,68.90,42.67,33.54,31.41,20.57,19.03,19.00,14.00.ATR-FTIR(cm-1):3257,
2958,2927,2871,1635,1590,1527,1462,1361,1274,1238,1163,1048,746.ESI-MS:
calculated[C16H24N2O+H]+:261.1961,found:261.1967.[α]20D＝+9.7(c＝0.98,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:1mL/min),t1(minor)＝
3.8min,t2(major)＝4.9min.。
6.4Hz,2H),1.78–1.63(m,3H),1.55–1.44(m,2H),1.03(d,J＝6.7Hz,3H),0.99–0.92(m,
6H).13C NMR(101MHz,CDCl3)δ163.97,149.41,132.43,129.91,113.98,110.27,108.37,
73.10,68.90,42.67,33.54,31.41,20.57,19.03,19.00,14.00.ATR-FTIR(cm-1):3257,
2958,2927,2871,1635,1590,1527,1462,1361,1274,1238,1163,1048,746.ESI-MS:
calculated[C16H24N2O+H]+:261.1961,found:261.1967.[α]20D＝+9.7(c＝0.98,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝98/2,detector:254nm,flow rate:1mL/min),t1(minor)＝
3.8min,t2(major)＝4.9min.。
[0170] 实施例38：(R)-[1,1'-联萘]-2,2'-二胺的制备(4a)
[0171]
[0172] 在空气环境下，在反应管中加入1a(0.2mmol),2b(0.6mmol),碳酸钾(0.6mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钾(2.5mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4a。
[0173] 产物收率82％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.82–7.76(m,4H),7.25–7.17(m,4H),7.13(d,J＝8.8Hz,2H),7.07(d,J＝8.1Hz,2H),3.67(br s,4H).13C NMR(101MHz,CDCl3)δ142.84,133.81,129.62,128.58,128.28,126.97,124.07,122.56,
118.45,112.69.ATR-FTIR(cm-1):3472,3376,2926,1618,1508,1467,1383,816,751.ESI-MS:calculated[C20H16N2+H]+:285.1386,found:285.1392.[α]20D＝+109.2(c＝0.84,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝8.0min,t2(minor)＝18.3min.。
118.45,112.69.ATR-FTIR(cm-1):3472,3376,2926,1618,1508,1467,1383,816,751.ESI-MS:calculated[C20H16N2+H]+:285.1386,found:285.1392.[α]20D＝+109.2(c＝0.84,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝8.0min,t2(minor)＝18.3min.。
[0174] 实施例39：(R)-3,3'-二苯基-[1,1'-联萘]-2,2'-二胺的制备(4b)
[0175]
[0176] 在空气环境下，在反应管中加入(R)-3,3'-二苯基-[1,1'-二萘]-2,2'-二醇(0.2mmol),2b(1.2mmol),碳酸钾(1.2mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至100℃的油浴锅中搅拌48h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钾(2.5mmol),然后放入预先升温至150℃的油浴锅中搅拌36h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4b。
[0177] 产物收率85％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.79(d,J＝8.3Hz,2H),7.76(s,2H),7.65–7.55(m,4H),7.46(t,J＝7.5Hz,4H),7.38(t,J＝7.3Hz,2H),7.25–7.19(m,4H),7.17–7.10(m,2H),3.86(br s,4H).13C NMR(101MHz,CDCl3)δ140.91,139.38,
133.24,130.89,129.91,129.48,128.98,128.39,128.30,127.79,126.93,123.98,122.76,
113.15.ATR-FTIR(cm-1):3479,3382,3054,2925,2854,1621,1604,1495,1427,1227,1024,
785,748,703.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2017.[α]20D＝+71.5(c＝0.72,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝80/20,detector:254nm,flow rate:1mL/min),t1(major)＝5.2min,t2(minor)＝6.9min.。
133.24,130.89,129.91,129.48,128.98,128.39,128.30,127.79,126.93,123.98,122.76,
113.15.ATR-FTIR(cm-1):3479,3382,3054,2925,2854,1621,1604,1495,1427,1227,1024,
785,748,703.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2017.[α]20D＝+71.5(c＝0.72,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝80/20,detector:254nm,flow rate:1mL/min),t1(major)＝5.2min,t2(minor)＝6.9min.。
[0178] 实施例40：(R)-3,3'-二甲基-[1,1'-联萘]-2,2'-二胺的制备(4c)
[0179]
[0180] 在空气环境下，在反应管中加入(R)-3,3'-二苯基-[1,1'-二萘]-2,2'-二醇(0.2mmol),2b(0.6mmol),碳酸钾(0.6mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钠(2.5mmol),然后放入预先升温至130℃的油浴锅中搅拌4h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4c。
[0181] 产物收率90％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.76(d,J＝8.0Hz,2H),7.71(s,2H),7.23(t,J＝7.4Hz,2H),7.15(t,J＝7.5Hz,2H),7.02(d,J＝8.3Hz,2H),3.66(br s,4H),2.45(s,6H).13C NMR(101MHz,CDCl3)δ142.28,132.60,129.05,128.52,127.49,
125.98,125.35,123.96,122.52,112.94,18.61.ATR-FTIR(cm-1):3474,3386,2924,2853,
1628,1433,1405,1098,748.ESI-MS:calculated[C22H20N2+H]+:313.1699,found:313.1711.[α]20D＝+90.6(c＝0.73,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(major)＝13.4min,t2(minor)＝23.9min.。
125.98,125.35,123.96,122.52,112.94,18.61.ATR-FTIR(cm-1):3474,3386,2924,2853,
1628,1433,1405,1098,748.ESI-MS:calculated[C22H20N2+H]+:313.1699,found:313.1711.[α]20D＝+90.6(c＝0.73,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(major)＝13.4min,t2(minor)＝23.9min.。
[0182] 实施例41：(R)-6,6'-二苯基-[1,1'-联萘]-2,2'-二胺的制备(4d)
[0183]
[0184] (R)-6,6'-二苯基-[1,1'-二萘]-2,2'-二醇和2b作为反应的起始底物制备目标产物4d，制备方法与实施例38相同。
[0185] 产物收率88％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ8.04(d,J＝1.5Hz,2H),7.89(d,J＝8.8Hz,2H),7.68(d,J＝7.4Hz,4H),7.51(dd,J＝8.7,1.7Hz,2H),7.46(t,J＝
7.6Hz,4H),7.34(t,J＝7.3Hz,2H),7.24–7.16(m,4H),3.49(br s,4H).13C NMR(101MHz,CDCl3)δ143.02,141.37,135.31,133.04,130.04,128.89,128.81,127.21,126.98,126.62,
126.33,124.63,118.90,112.44.ATR-FTIR(cm-1):3470,3378,2921,2851,1620,1493,1386,
1360,1264,758,738,699.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2013.[α]20D＝-133.3(c＝1.06,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝18.2min,t2(minor)＝31.2min.。
7.6Hz,4H),7.34(t,J＝7.3Hz,2H),7.24–7.16(m,4H),3.49(br s,4H).13C NMR(101MHz,CDCl3)δ143.02,141.37,135.31,133.04,130.04,128.89,128.81,127.21,126.98,126.62,
126.33,124.63,118.90,112.44.ATR-FTIR(cm-1):3470,3378,2921,2851,1620,1493,1386,
1360,1264,758,738,699.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2013.[α]20D＝-133.3(c＝1.06,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝18.2min,t2(minor)＝31.2min.。
[0186] 实施例42：(R)-N2，N2'-二甲基-[1,1'-联萘]-2,2'-二胺的制备(4e)[0187]
[0188] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2ba作为反应的起始底物制备目标产物4e，制备方法与实施例40相同。
[0189] 产物收率80％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.90(d,J＝8.9Hz,2H),7.78(d,J＝7.6Hz,2H),7.24(d,J＝8.9Hz,2H),7.20–7.11(m,4H),6.96(d,J＝8.1Hz,2H),
3.66(br s,2H),2.80(s,6H).13C NMR(101MHz,CDCl3)δ145.65,133.75,129.71,128.19,
127.64,126.75,123.72,121.81,113.47,111.76,31.12.ATR-FTIR(cm-1):3417,3051,2924,
2821,1616,1597,1512,1420,1340,1300,1169,1152,811,747.ESI-MS:calculated[C22H20N2+H]+:313.1699,found:313.1702.[α]20D＝+134.1(c＝0.99,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝7.1min,t2(major)＝
9.5min.。
3.66(br s,2H),2.80(s,6H).13C NMR(101MHz,CDCl3)δ145.65,133.75,129.71,128.19,
127.64,126.75,123.72,121.81,113.47,111.76,31.12.ATR-FTIR(cm-1):3417,3051,2924,
2821,1616,1597,1512,1420,1340,1300,1169,1152,811,747.ESI-MS:calculated[C22H20N2+H]+:313.1699,found:313.1702.[α]20D＝+134.1(c＝0.99,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝7.1min,t2(major)＝
9.5min.。
[0190] 实施例43：(R)-N2，N2'-二乙基-[1,1'-联萘]-2,2'-二胺的制备(4f)[0191]
[0192] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bb作为反应的起始底物制备目标产物4f，制备方法与实施例38相同。
[0193] 产物收率74％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.88(d,J＝8.9Hz,2H),7.77(d,J＝7.7Hz,2H),7.26(d,J＝9.0Hz,2H),7.20–7.11(m,4H),6.96(d,J＝8.2Hz,2H),
3.60(br s,2H),3.21(q,J＝7.0Hz,4H),1.02(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ
144.73,134.03,129.67,128.16,127.78,126.75,123.97,121.96,114.33,112.30,38.73,
15.36.ATR-FTIR(cm-1):3402,3052,2967,2926,1617,1598,1511,1424,1336,1302,1152,
809,747.ESI-MS:calculated[C24H24N2+H]+:341.2012,found:341.2014.[α]20D＝+91.4(c＝
0.83,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝6.2min.。
3.60(br s,2H),3.21(q,J＝7.0Hz,4H),1.02(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ
144.73,134.03,129.67,128.16,127.78,126.75,123.97,121.96,114.33,112.30,38.73,
15.36.ATR-FTIR(cm-1):3402,3052,2967,2926,1617,1598,1511,1424,1336,1302,1152,
809,747.ESI-MS:calculated[C24H24N2+H]+:341.2012,found:341.2014.[α]20D＝+91.4(c＝
0.83,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝6.2min.。
[0194] 实施例44：(R)-N2，N2'-二丙基-[1,1'-联萘]-2,2'-二胺的制备(4g)[0195]
[0196] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bc作为反应的起始底物制备目标产物4g，制备方法与实施例40相同。
[0197] 产物收率72％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.86(d,J＝9.0Hz,2H),7.76(d,J＝7.5Hz,2H),7.24(d,J＝9.0Hz,2H),7.18–7.10(m,4H),6.97(d,J＝8.1Hz,2H),
3.70(br s,2H),3.11(t,J＝6.9Hz,4H),1.45–1.34(m,4H),0.73(t,J＝7.4Hz,6H).13C NMR(101MHz,CDCl3)δ144.80,134.04,129.62,128.15,127.66,126.73,123.94,121.85,-1
114.21,112.00,45.94,23.07,11.38.ATR-FTIR(cm ):3407,3052,2959,2928,2873,1617,
1597,1511,1425,1336,1151,810,746.ESI-MS:calculated[C26H28N2+H]+:369.2325,found:
369.2332.[α]20D＝+120.2(c＝0.80,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.1min,t2(major)＝4.7min.。
3.70(br s,2H),3.11(t,J＝6.9Hz,4H),1.45–1.34(m,4H),0.73(t,J＝7.4Hz,6H).13C NMR(101MHz,CDCl3)δ144.80,134.04,129.62,128.15,127.66,126.73,123.94,121.85,-1
114.21,112.00,45.94,23.07,11.38.ATR-FTIR(cm ):3407,3052,2959,2928,2873,1617,
1597,1511,1425,1336,1151,810,746.ESI-MS:calculated[C26H28N2+H]+:369.2325,found:
369.2332.[α]20D＝+120.2(c＝0.80,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.1min,t2(major)＝4.7min.。
[0198] 实施例45：(R)-N2，N2'-二丁基-[1,1'-联萘]-2,2'-二胺的制备(4h)[0199]
[0200] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bd作为反应的起始底物制备目标产物4h，制备方法与实施例38相同。
[0201] 产物收率56％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.9Hz,2H),7.76(d,J＝7.6Hz,2H),7.24(d,J＝8.9Hz,2H),7.19–7.10(m,4H),6.96(d,J＝7.9Hz,2H),
3.66(br s,2H),3.14(t,J＝7.1Hz,4H),1.41–1.31(m,4H),1.20–1.10(m,4H),0.78(t,J＝
7.3Hz,6H).13C NMR(101MHz,CDCl3)δ144.78,134.03,129.63,128.14,127.67,126.71,
123.94,121.86,114.22,112.05,43.91,32.03,20.09,13.91.ATR-FTIR(cm-1):3407,3053,
2956,2928,2871,1618,1597,1512,1425,1338,1297,1151,809,746.ESI-MS:calculated[C28H32N2+H]+:397.2638,found:397.2639.[α]20D＝+108.4(c＝1.0,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:0.2mL/min),t1(minor)＝20.9min,t2(major)＝26.6min.。
3.66(br s,2H),3.14(t,J＝7.1Hz,4H),1.41–1.31(m,4H),1.20–1.10(m,4H),0.78(t,J＝
7.3Hz,6H).13C NMR(101MHz,CDCl3)δ144.78,134.03,129.63,128.14,127.67,126.71,
123.94,121.86,114.22,112.05,43.91,32.03,20.09,13.91.ATR-FTIR(cm-1):3407,3053,
2956,2928,2871,1618,1597,1512,1425,1338,1297,1151,809,746.ESI-MS:calculated[C28H32N2+H]+:397.2638,found:397.2639.[α]20D＝+108.4(c＝1.0,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝95/5,detector:254nm,flow rate:0.2mL/min),t1(minor)＝20.9min,t2(major)＝26.6min.。
[0202] 实施例46：(R)-N2，N2'-双十二烷基-[1,1'-联萘]-2,2'-二胺的制备(4i)[0203]
[0204] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2be作为反应的起始底物制备目标产物4i，制备方法与实施例40相同。
[0205] 产物收率74％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.86(d,J＝9.0Hz,2H),7.76(d,J＝7.7Hz,2H),7.24(d,J＝9.2Hz,2H),7.19–7.10(m,4H),6.96(d,J＝8.1Hz,2H),
3.67(br s,2H),3.13(t,J＝6.8Hz,4H),1.41–1.33(m,4H),1.30–1.07(m,36H),0.88(t,J＝
6.6Hz,6H).13C NMR(101MHz,CDCl3)δ144.84,134.05,129.62,128.14,127.67,126.72,
123.95,121.85,114.23,112.06,44.21,32.07,29.92,29.81,29.78,29.71,29.50,26.97,
22.84,14.27.ATR-FTIR(cm-1):3408,3053,2924,2853,1618,1598,1467,1425,1338,1299,
1150,808,745.ESI-MS:calculated[C44H64N2+H]+:621.5142,found:621.5136.[α]20D＝+
67.2(c＝0.94,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(major)＝11.2min,t2(minor)＝14.3min.。
3.67(br s,2H),3.13(t,J＝6.8Hz,4H),1.41–1.33(m,4H),1.30–1.07(m,36H),0.88(t,J＝
6.6Hz,6H).13C NMR(101MHz,CDCl3)δ144.84,134.05,129.62,128.14,127.67,126.72,
123.95,121.85,114.23,112.06,44.21,32.07,29.92,29.81,29.78,29.71,29.50,26.97,
22.84,14.27.ATR-FTIR(cm-1):3408,3053,2924,2853,1618,1598,1467,1425,1338,1299,
1150,808,745.ESI-MS:calculated[C44H64N2+H]+:621.5142,found:621.5136.[α]20D＝+
67.2(c＝0.94,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(major)＝11.2min,t2(minor)＝14.3min.。
[0206] 实施例47：(R)-N2，N2'-双十六烷基-[1,1'-联萘]-2,2'-二胺的制备(4j)[0207]
[0208] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bf作为反应的起始底物制备目标产物4j，制备方法与实施例40相同。
[0209] 产物收率68％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.87(d,J＝9.0Hz,2H),7.76(d,J＝7.6Hz,2H),7.24(d,J＝9.0Hz,2H),7.19–7.10(m,4H),6.96(d,J＝8.1Hz,2H),
3.66(br s,2H),3.13(t,J＝6.7Hz,4H),1.41–1.33(m,4H),1.29–1.10(m,52H),0.88(t,J＝
6.6Hz,6H).13C NMR(101MHz,CDCl3)δ144.85,134.05,129.62,128.15,127.68,126.73,
123.96,121.86,114.24,112.07,44.22,32.09,29.92,29.87,29.84,29.83,29.72,29.71,
29.53,29.50,26.98,22.85,14.27.ATR-FTIR(cm-1):3409,3054,2924,2853,1619,1598,
1466,1425,1338,1299,1150,808,745.ESI-MS:calculated[C52H80N2+H]+:733.6394,found:
733.6407.[α]20D＝+58.1(c＝0.97,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(minor)＝8.5min,t2(major)＝10.7min.。
3.66(br s,2H),3.13(t,J＝6.7Hz,4H),1.41–1.33(m,4H),1.29–1.10(m,52H),0.88(t,J＝
6.6Hz,6H).13C NMR(101MHz,CDCl3)δ144.85,134.05,129.62,128.15,127.68,126.73,
123.96,121.86,114.24,112.07,44.22,32.09,29.92,29.87,29.84,29.83,29.72,29.71,
29.53,29.50,26.98,22.85,14.27.ATR-FTIR(cm-1):3409,3054,2924,2853,1619,1598,
1466,1425,1338,1299,1150,808,745.ESI-MS:calculated[C52H80N2+H]+:733.6394,found:
733.6407.[α]20D＝+58.1(c＝0.97,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(minor)＝8.5min,t2(major)＝10.7min.。
[0210] 实施例48：(R)-N2，N2'-二苄基-[1,1'-联萘]-2,2'-二胺的制备(4k)[0211]
[0212] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bj作为反应的起始底物制备目标产物4k，制备方法与实施例40相同。
[0213] 产物收率54％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.78(d,J＝8.9Hz,2H),7.76–7.71(m,2H),7.22–7.12(m,16H),7.07–7.02(m,2H),4.41–4.34(m,4H),4.33–4.26(m,
2H).13C NMR(101MHz,CDCl3)δ144.35,139.95,133.95,129.78,128.58,128.25,127.86,
127.02,126.89,126.85,124.04,122.14,114.29,112.10,47.69.ATR-FTIR(cm-1):3419,
3055,2924,2854,1618,1597,1510,1495,1425,1338,1296,1150,810,738,697.ESI-MS:
calculated[C34H28N2+H]+:465.2325,found:465.2332.[α]20D＝+63.9(c＝0.70,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(major)＝7.4min,t2(minor)＝8.4min.。
2H).13C NMR(101MHz,CDCl3)δ144.35,139.95,133.95,129.78,128.58,128.25,127.86,
127.02,126.89,126.85,124.04,122.14,114.29,112.10,47.69.ATR-FTIR(cm-1):3419,
3055,2924,2854,1618,1597,1510,1495,1425,1338,1296,1150,810,738,697.ESI-MS:
calculated[C34H28N2+H]+:465.2325,found:465.2332.[α]20D＝+63.9(c＝0.70,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(major)＝7.4min,t2(minor)＝8.4min.。
[0214] 实施例49：(R)-N2，N2'-双(3-甲氧基丙基)-[1,1'-联萘]-2,2'-二胺的制备(4l)[0215]
[0216] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bg作为反应的起始底物制备目标产物4l，制备方法与实施例40相同。
[0217] 产物收率57％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.87(d,J＝9.0Hz,2H),7.80–7.73(m,2H),7.26(d,J＝9.0Hz,2H),7.19–7.10(m,4H),7.00–6.93(m,2H),3.90(br s,2H),3.27(t,J＝6.7Hz,4H),3.24–3.14(m,4H),3.01(s,6H),1.70–1.63(m,4H).13C NMR(101MHz,CDCl3)δ144.77,134.03,129.63,128.17,127.70,126.71,123.92,121.84,
114.07,112.17,70.47,58.51,41.44,29.65.ATR-FTIR(cm-1):3369,3052,2923,2855,1617,
1597,1511,1426,1337,1302,1117,811,747.ESI-MS:calculated[C28H32N2O2+H]+:
429.2536,found:429.2542.[α]20D＝+99.4(c＝0.83,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99/1,detector:254nm,flow rate:1mL/min),t1(major)＝15.5min,t2(minor)＝
18.3min.。
114.07,112.17,70.47,58.51,41.44,29.65.ATR-FTIR(cm-1):3369,3052,2923,2855,1617,
1597,1511,1426,1337,1302,1117,811,747.ESI-MS:calculated[C28H32N2O2+H]+:
429.2536,found:429.2542.[α]20D＝+99.4(c＝0.83,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99/1,detector:254nm,flow rate:1mL/min),t1(major)＝15.5min,t2(minor)＝
18.3min.。
[0218] 实施例50：(R)-N2，N2'-二苯基-[1,1'-联萘]-2,2'-二胺的制备(4m)[0219]
[0220] (R)-[1,1'-二萘]-2,2'-二醇(1a)和2bi作为反应的起始底物制备目标产物4m，制备方法与实施例40相同。
[0221] 产物收率45％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.87(d,J＝9.0Hz,2H),7.83(d,J＝8.0Hz,2H),7.67(d,J＝9.0Hz,2H),7.33–7.27(m,2H),7.25–7.13(m,8H),7.00–
6.85(m,6H).13C NMR(101MHz,CDCl3)δ142.62,140.49,134.10,129.56,129.53,129.37,
128.35,127.18,124.58,123.60,122.30,120.09,117.98,116.50.ATR-FTIR(cm-1):3395,
3051,2924,2853,1619,1595,1499,1417,1342,1301,812,739,693.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2015.[α]20D＝+43.8(c＝0.74,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.3min,t2(major)＝6.3min.。
6.85(m,6H).13C NMR(101MHz,CDCl3)δ142.62,140.49,134.10,129.56,129.53,129.37,
128.35,127.18,124.58,123.60,122.30,120.09,117.98,116.50.ATR-FTIR(cm-1):3395,
3051,2924,2853,1619,1595,1499,1417,1342,1301,812,739,693.ESI-MS:calculated[C32H24N2+H]+:437.2012,found:437.2015.[α]20D＝+43.8(c＝0.74,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝4.3min,t2(major)＝6.3min.。
[0222] 实施例51：(R)-N2，N2'-二异丁基-[1,1'-联萘]-2,2'-二胺的制备(4n)[0223]
[0224] 在空气环境下，在反应管中加入(R)-[1,1'-二萘]-2,2'-二醇(1a)(0.2mmol),2b(0.6mmol),碳酸钾(0.6mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钠(2.5mmol),然后放入预先升温至110℃的油浴锅中搅拌3h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4n。
[0225] 产物收率58％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.86(d,J＝9.0Hz,2H),7.80–7.74(m,2H),7.24(d,J＝9.0Hz,2H),7.19–7.11(m,4H),7.01–6.96(m,2H),3.78(br s,2H),2.95(d,J＝6.8Hz,4H),1.73–1.62(m,2H),0.71(t,J＝6.2Hz,12H).13C NMR(101MHz,CDCl3)δ144.82,134.06,129.58,128.13,127.53,126.72,123.93,121.77,114.06,111.71,
51.81,28.40,20.28,20.27.ATR-FTIR(cm-1):3412,3054,2925,2855,1619,1598,1513,
1464,1377,1335,1152,808,745.ESI-MS:calculated[C28H32N2+H]+:397.2638,found:
397.2644.[α]20D＝+99.4(c＝0.83,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(major)＝10.2min,t2(minor)＝13.6min.。
51.81,28.40,20.28,20.27.ATR-FTIR(cm-1):3412,3054,2925,2855,1619,1598,1513,
1464,1377,1335,1152,808,745.ESI-MS:calculated[C28H32N2+H]+:397.2638,found:
397.2644.[α]20D＝+99.4(c＝0.83,CH2Cl2).HPLC:(ID,hexane/i-PrOH＝99.94/0.06,detector:254nm,flow rate:1mL/min),t1(major)＝10.2min,t2(minor)＝13.6min.。
[0226] 实施例52：(R)-N2，N2'，3,3'-四甲基-[1,1'-联萘]-2,2'-二胺的制备(4o)[0227]
[0228] (R)-3,3'-二甲基-[1,1'-联萘]-2,2'-二醇和2ba作为反应的起始底物制备目标产物4o，制备方法与实施例51相同。
[0229] 产物收率70％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.76–7.71(m,4H),7.27–7.23(m,2H),7.15–7.10(m,2H),6.99(d,J＝8.4Hz,2H),3.04(br s,2H),2.57(s,6H),
2.51(s,6H).13C NMR(101MHz,CDCl3)δ146.82,133.13,130.36,129.66,129.59,127.17,
125.83,125.04,123.57,119.92,35.29,20.12.ATR-FTIR(cm-1):3453,3364,2925,2857,
1622,1479,1443,1403,1265,1123,750.ESI-MS:calculated[C24H24N2+H]+:341.2012,found:341.2013.[α]20D＝+132.4(c＝0.78,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99/1,detector:254nm,flow rate:0.5mL/min),t1(minor)＝11.6min,t2(major)＝13.4min.。
2.51(s,6H).13C NMR(101MHz,CDCl3)δ146.82,133.13,130.36,129.66,129.59,127.17,
125.83,125.04,123.57,119.92,35.29,20.12.ATR-FTIR(cm-1):3453,3364,2925,2857,
1622,1479,1443,1403,1265,1123,750.ESI-MS:calculated[C24H24N2+H]+:341.2012,found:341.2013.[α]20D＝+132.4(c＝0.78,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝99/1,detector:254nm,flow rate:0.5mL/min),t1(minor)＝11.6min,t2(major)＝13.4min.。
[0230] 实施例53：(R)-2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3,3'-二胺的制备(4p)[0231]
[0232] 在空气环境下，在反应管中加入(R)-2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3,3'-二醇(0.2mmol),2b(0.6mmol),碳酸钾(0.6mmol)，碘化钾(0.02mmol)，二甲基亚砜(2ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在反应管中加入氢氧化钠(2.5mmol),然后放入预先升温至90℃的油浴锅中搅拌3h，反应结束后，待反应管冷却至室温，加入5ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4p。
[0233] 产物收率77％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.62(d,J＝8.2Hz,2H),7.29(t,J＝7.4Hz,2H),7.18(s,2H),7.08(d,J＝8.4Hz,2H),7.01(t,J＝7.5Hz,2H),4.61(d,J＝5.7Hz,2H),4.57(d,J＝5.7Hz,2H),4.31(br s,4H),3.03(s,6H).13C NMR(101MHz,CDCl3)δ144.85,139.92,132.24,128.08,126.23,125.78,125.69,125.48,122.98,110.17,
99.02,57.13.ATR-FTIR(cm-1):3467,3371,3055,2925,2853,1624,1504,1468,1384,1249,
1152,1073,972,920,748.ESI-MS:calculated[C24H24N2O4+H]+:405.1808,found:405.1803.[α]20D＝-66.4(c＝1.07,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝14.6min,t2(minor)＝38.5min.。
99.02,57.13.ATR-FTIR(cm-1):3467,3371,3055,2925,2853,1624,1504,1468,1384,1249,
1152,1073,972,920,748.ESI-MS:calculated[C24H24N2O4+H]+:405.1808,found:405.1803.[α]20D＝-66.4(c＝1.07,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(major)＝14.6min,t2(minor)＝38.5min.。
[0234] 实施例54：(R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二胺的制备(4q)[0235]
[0236] (R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二醇和2b作为反应的起始底物制备目标产物4q，制备方法与实施例38相同。
[0237] 产物收率62％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.05(t,J＝7.6Hz,2H),6.71(d,J＝7.4Hz,2H),6.44(d,J＝7.8Hz,2H),3.45(br s,4H),3.04–2.91(m,4H),2.27–
2.15(m,4H).13C NMR(101MHz,CDCl3)δ145.14,143.37,129.96,128.77,115.29,113.41,
58.91,35.47,31.17.ATR-FTIR(cm-1):3457,3367,3029,2930,2847,1614,1589,1474,1300,
776,745.ESI-MS:calculated[C17H18N2+H]+:251.1542,found:251.1549.[α]20D＝+114.5(c＝1.01,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝5.7min,t2(major)＝8.0min.。
2.15(m,4H).13C NMR(101MHz,CDCl3)δ145.14,143.37,129.96,128.77,115.29,113.41,
58.91,35.47,31.17.ATR-FTIR(cm-1):3457,3367,3029,2930,2847,1614,1589,1474,1300,
776,745.ESI-MS:calculated[C17H18N2+H]+:251.1542,found:251.1549.[α]20D＝+114.5(c＝1.01,CH2Cl2).HPLC:(AD-H,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝5.7min,t2(major)＝8.0min.。
[0238] 实施例55：(R)-N7，N7'二甲基-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二胺的制备(4r)
[0239]
[0240] (R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二醇和2ba作为反应的起始底物制备目标产物4r，制备方法与实施例38相同。
[0241] 产物收率79％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.17(t,J＝7.7Hz,2H),6.68(d,J＝7.2Hz,2H),6.43(d,J＝7.9Hz,2H),3.54(br s,2H),3.05–2.89(m,4H),2.65(s,
6H),2.19–2.12(m,4H).13C NMR(101MHz,CDCl3)δ146.45,144.53,129.02,113.92,107.62,
58.98,35.22,31.13,30.70.ATR-FTIR(cm-1):3410,2935,2812,1591,1503,1475,1311,
1159,1089,772,739.ESI-MS:calculated[C19H22N2+H]+:279.1855,found:279.1861.[α]20D＝+180.6(c＝1.02,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝3.7min,t2(major)＝4.7min.。
6H),2.19–2.12(m,4H).13C NMR(101MHz,CDCl3)δ146.45,144.53,129.02,113.92,107.62,
58.98,35.22,31.13,30.70.ATR-FTIR(cm-1):3410,2935,2812,1591,1503,1475,1311,
1159,1089,772,739.ESI-MS:calculated[C19H22N2+H]+:279.1855,found:279.1861.[α]20D＝+180.6(c＝1.02,CH2Cl2).HPLC:(OD-H,hexane/i-PrOH＝90/10,detector:254nm,flow rate:1mL/min),t1(minor)＝3.7min,t2(major)＝4.7min.。
[0242] 实施例56：(R)-N7，N7'二乙基-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二胺的制备(4s)
[0243]
[0244] (R)-2,2'，3,3'-四氢-1,1'-螺双[茚]-7,7'二醇和2bb作为反应的起始底物制备目标产物4s，制备方法与实施例38相同。
[0245] 产物收率58％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.12(t,J＝7.7Hz,2H),6.65(d,J＝7.4Hz,2H),6.39(d,J＝8.0Hz,2H),3.38(br s,2H),3.04–2.95(m,4H),2.93–
2.86(m,4H),2.20–2.12(m,4H),0.86(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ145.51,
144.57,128.98,128.76,113.73,107.89,58.92,38.25,35.24,31.22,14.49.ATR-FTIR(cm-1):3388,2927,2853,1592,1503,1473,1326,1308,1154,772.ESI-MS:calculated[C21H26N2+H]+:307.2168,found:307.2172.[α]20D＝+205.1(c＝0.49,CH2Cl2).HPLC:(IE,hexane/i-PrOH＝99/1,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝
5.1min.。
2.86(m,4H),2.20–2.12(m,4H),0.86(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ145.51,
144.57,128.98,128.76,113.73,107.89,58.92,38.25,35.24,31.22,14.49.ATR-FTIR(cm-1):3388,2927,2853,1592,1503,1473,1326,1308,1154,772.ESI-MS:calculated[C21H26N2+H]+:307.2168,found:307.2172.[α]20D＝+205.1(c＝0.49,CH2Cl2).HPLC:(IE,hexane/i-PrOH＝99/1,detector:254nm,flow rate:1mL/min),t1(minor)＝4.4min,t2(major)＝
5.1min.。
[0246] 实施例57：(S)-2'-氨基-[1,1'-联萘]-2-醇的制备(3a’)
[0247]
[0248] (S)-[1,1'-二萘]-2,2'-二醇(1a')和2e作为反应的起始底物制备目标产物(S)-2'-氨基-[1,1'-联萘]-2-醇(3a')，制备方法与实施例1相同。
[0249] 产物收率71％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.92(d,J＝9.0Hz,1H),7.87(d,J＝8.0Hz,1H),7.84(d,J＝8.8Hz,1H),7.80(d,J＝7.8Hz,1H),7.39–7.31(m,2H),
7.30–7.20(m,3H),7.17(d,J＝8.4Hz,1H),7.13(d,J＝8.8Hz,1H),7.04(d,J＝8.0Hz,1H),
5.14(br s,1H),3.72(br s,2H).13C NMR(101MHz,CDCl3)δ151.95,143.87,134.25,133.32,
130.74,130.49,129.64,128.49,128.44,128.38,127.45,127.10,124.67,123.86,123.78,
122.89,118.30,117.84,114.39,108.64.ATR-FTIR(cm-1):3396,2923,1617,1508,1382,
1268,821,732.ESI-MS:calculated[C20H15NO+H]+:286.1226,found:286.1235.[α]20D＝-
36.1(c＝1.0,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝80/20,detector:254nm,flow rate:
1mL/min),t1(minor)＝16.6min,t2(major)＝21.2min.。
7.30–7.20(m,3H),7.17(d,J＝8.4Hz,1H),7.13(d,J＝8.8Hz,1H),7.04(d,J＝8.0Hz,1H),
5.14(br s,1H),3.72(br s,2H).13C NMR(101MHz,CDCl3)δ151.95,143.87,134.25,133.32,
130.74,130.49,129.64,128.49,128.44,128.38,127.45,127.10,124.67,123.86,123.78,
122.89,118.30,117.84,114.39,108.64.ATR-FTIR(cm-1):3396,2923,1617,1508,1382,
1268,821,732.ESI-MS:calculated[C20H15NO+H]+:286.1226,found:286.1235.[α]20D＝-
36.1(c＝1.0,CH2Cl2).HPLC:(OJ-H,hexane/i-PrOH＝80/20,detector:254nm,flow rate:
1mL/min),t1(minor)＝16.6min,t2(major)＝21.2min.。
[0250] 实施例58：(S)-[1,1'-联萘]-2,2'-二胺的制备的制备(4a’)
[0251]
[0252] (S)-[1,1'-二萘]-2,2'-二醇(1a')和2b作为反应的起始底物制备目标产物(S)-[1,1'-联萘]-2,2'-二胺(4a')，制备方法与实施例38相同。
[0253] 产物收率82％；黄色固体；99％ee；1H NMR(400MHz,CDCl3)δ7.82–7.76(m,4H),7.25–7.17(m,4H),7.13(d,J＝8.8Hz,2H),7.07(d,J＝8.1Hz,2H),3.67(br s,4H).13C NMR(101MHz,CDCl3)δ142.84,133.81,129.62,128.58,128.28,126.97,124.07,122.56,
118.45,112.69.ATR-FTIR(cm-1):3466,3372,2925,2855,1618,1508,1383,816,749.ESI-MS:calculated[C20H16N2+H]+:285.1386,found:285.1393.[α]20D＝-106.3(c＝0.83,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝7.9min,t2(major)＝18.0min.。
118.45,112.69.ATR-FTIR(cm-1):3466,3372,2925,2855,1618,1508,1383,816,749.ESI-MS:calculated[C20H16N2+H]+:285.1386,found:285.1393.[α]20D＝-106.3(c＝0.83,CH2Cl2).HPLC:(IA,hexane/i-PrOH＝70/30,detector:254nm,flow rate:1mL/min),t1(minor)＝7.9min,t2(major)＝18.0min.。
[0254] 实施例59：(R)-[1,1'-联萘]-2,2'-二胺的克级制备过程(4a)
[0255]
[0256] 在空气环境下，在100ml圆底烧瓶中加入1a(5mmol),2b(15mmol),碳酸钾(15mmol)，碘化钾(0.5mmol)，二甲基亚砜(40ml)作为反应溶剂，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在圆底烧瓶中加入氢氧化钾(60mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待圆底烧瓶冷却至室温，加入40ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4a。
[0257] 产物收率82％；黄色固体；99％ee。
[0258] 实施例60：(R)-[1,1'-联萘]-2,2'-二胺的十克级制备过程(4a)
[0259] 在空气环境下，在1000ml圆底烧瓶中加入1a(50mmol),2b(150mmol),碳酸钾(150mmol)，碘化钾(5mmol)，二甲基亚砜(400ml)作为反应溶剂，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失并且全部转化成双烷基化产物，将反应管从油浴锅中提起，直接在圆底烧瓶中加入氢氧化钾(600mmol),然后放入预先升温至150℃的油浴锅中搅拌4h，反应结束后，待圆底烧瓶冷却至室温，重结晶得到目标产物4a。
[0260] 产物收率71％；黄色固体；99％ee。
[0261] 实施例61：(R)-[1,1'-联萘]-2,2'-二胺的百克级制备过程(4a)
[0262] 在空气环境下，在5000ml圆底烧瓶中加入1a(500mmol),2b(1500mmol),碳酸钾(1500mmol)，碘化钾(50mmol)，二甲基亚砜(2500ml)作为反应溶剂，放入预先升温至50℃的机械搅拌器中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1a完全消失并且全部转化成双烷基化产物，直接在烧瓶中加入氢氧化钾(6000mmol),然后放入升温至150℃的油浴中搅拌4h，反应结束后，待烧瓶冷却至室温，重结晶得到目标产物4a。
[0263] 产物收率70％；黄色固体；99％ee。
[0264] 实施例62：(R)-2'-乙氧基-N-甲基-[1,1'-联萘]-2-胺的克级制备(3ad)[0265]
[0266] 在空气环境下，在100ml圆底烧瓶中加入2'-乙氧基-[1,1'-联萘]-2-醇(3.18mmol),2ba(4.77mmol),碳酸钾(6.36mmol)，碘化钾(0.32mmol)，二甲基亚砜(30ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失后，将反应管从油浴锅中提起，直接在圆底烧瓶中加入氢氧化钠(40mmol),然后放入预先升温至130℃的油浴锅中搅拌4h，反应结束后，待圆底烧瓶冷却至室温，加入30ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物3ad。
[0267] 产物收率91％；黄色固体；99％ee。
[0268] 实施例63：(R)-N2，N2'-二甲基-[1,1'-联萘]-2,2'-二胺的克级制备(4e)[0269]
[0270] 在空气环境下，在100ml圆底烧瓶加入(R)-[1,1'-二萘]-2,2'-二醇(3.5mmol),2ba(10.5mmol),碳酸钾(10.5mmol)，碘化钾(0.35mmol)，二甲基亚砜(30ml)作为反应溶剂，在反应管上加上橡胶塞后，放入预先升温至50℃的油浴锅中搅拌24h。薄层色谱(TLC)点板确定反应终点，当TLC板显示反应原料1完全消失并且全部转化成双烷基化产物，直接在烧瓶中加入氢氧化钠(42mmol),然后放入预先升温至130℃的油浴锅中搅拌4h，反应结束后，待圆底烧瓶冷却至室温，加入30ml水淬灭反应，然后用乙酸乙酯萃取旋干，经柱层析分离得到目标产物4e。