CN112608274B - 一种手性胺化合物的催化合成方法及其化合物 - Google Patents

一种手性胺化合物的催化合成方法及其化合物 Download PDF

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CN112608274B
CN112608274B CN202011609045.0A CN202011609045A CN112608274B CN 112608274 B CN112608274 B CN 112608274B CN 202011609045 A CN202011609045 A CN 202011609045A CN 112608274 B CN112608274 B CN 112608274B
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郭其祥
朱芳
文巍
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Abstract

本发明公开了一种手性胺化合物的催化合成方法及其化合物，由甲胺化合物和肉桂醇衍生酯反应生成中间产物，该中间产物再与Boc2O反应生成手性胺化合物，该反应于碱性条件下，在钯催化剂和一种手性醛化合物的催化作用下进行，生成的手性胺化合物的分子结构中，手性碳原子上连接有胺基、烯丙基烷烃基和含氮不饱和杂环基团或稠杂环基团，其中含氮不饱和杂环基团或稠杂环基团为N原子的α位或β位取代基。本发明的有益效果：本方法工艺路线简单，反应条件温和，无外加保护基的条件下就能直接合成手性胺类化合物，该手性胺化合物可用于合成手性配体、手性有机催化剂以及生物活性分子。

Description

一种手性胺化合物的催化合成方法及其化合物
技术领域
本发明属于手性化合物制备技术领域，具体涉及一种手性胺化合物的催化合成方法及其化合物。
背景技术
手性胺类化合物在工业和医药领域具有广泛应用，用于合成手性配体、手性有机催化剂以及生物活性分子。通过手性金属催化剂对亚胺的催化氢化近来得到较多研究，例如专利文献CN109942506A公开了一种不对称镍催化氢化N-磺酰亚胺制备手性胺的方法，其在镍的手性催化剂的催化作用下，N-磺酰亚胺与氢气发生氢化反应生成手性胺。然而，对于含有不饱和链烃基的手性胺化合物，采用催化加氢方法则难以制备。该类化合物的手性合成主要通过亚胺的丙烯酰基化、氨基酸衍生烯丙醇酯的脱羧烯丙基化进行。然而，现有技术存在反应路线长、步骤多，或反应过程需要外加保护基团等不足。目前，大量研究仍在进行中，以寻找高效简便的合成手性胺类化合物的方法。
发明内容
有鉴于此，本发明的目的之一在于提供一种手性胺化合物的催化合成方法。
其技术方案如下：
一种手性胺化合物的催化合成方法，其关键在于，在钯催化剂和一种手性醛化合物的催化作用下，甲胺化合物和肉桂醇衍生酯于碱性条件下反应生成中间产物，该中间产物再与Boc2O反应生成所述手性胺化合物；
所述甲胺化合物的结构为
Figure BDA0002874193000000011
R1或为六元含氮不饱和杂环基团，或为苯并六元含氮不饱和杂环基团，且R1为N原子的α位或β位取代基；
所述肉桂醇衍生酯的结构为；
Figure BDA0002874193000000021
其中PG为4-CF3C6H4CO，R2选自H、取代或非取代的链烃基、取代或非取代的芳香基、取代或非取代的呋喃基、取代或非取代的噻吩基中的任意一种，R3为H或甲基；
所述手性胺化合物的结构如式(Ⅰ)：
Figure BDA0002874193000000022
在一种实施方式中，上述手性胺化合物的结构如式(Ⅱ)：
Figure BDA0002874193000000023
其中R3为H或甲基；
R2为H、-CH3、-CH2CH2CH3，或选自如下基团中的一种：
Figure BDA0002874193000000031
在一种实施方式中，上述手性胺化合物的结构如式(Ⅲ)：
Figure BDA0002874193000000041
其中R4选自以下基团中的任意一种：
Figure BDA0002874193000000042
在一种实施方式中，上述手性醛化合物或为
Figure BDA0002874193000000043
其中R5为H、TMS、4-FC6H4、4-MeOC6H4、4-CF3C6H4、3,5-2MeC6H3、3,5-2CF3C6H3中的一种，
或为
Figure BDA0002874193000000044
或为
Figure BDA0002874193000000051
或为
Figure BDA0002874193000000052
在一种实施方式中，催化合成方法按以下步骤进行：
步骤一、在保护气氛下，将钯催化剂和溶剂加入到干燥的反应容器中，搅拌溶解，再将所述甲胺化合物、肉桂醇衍生酯、手性醛化合物、反应助剂依次加入反应容器中，-40℃-80℃条件下反应，至肉桂醇衍生酯消耗完，反应结束后，分离得到中间产物，紧接着进行步骤二；
步骤二、向所述中间产物中依次加入Boc2O、Na2CO3，待反应结束后，分离得到所述手性胺化合物。
在一种实施方式中，上述溶剂为甲苯；
所述钯催化剂或由[Pd(C3H5)Cl]2、Pd(OAc)2、Pd(PPh3)4、Pd(CH3CN)2Cl2中的一种与dppp组成，或由[Pd(C3H5)Cl]2与dppf、dppb、PPh3、dppe中的一种组成；
所述反应助剂为路易斯酸和路易斯碱，其中所述路易斯酸选自ZnF2、Zn(OAc)2、Zn(OTf)2、ZnBr2、ZnCl2、Zn(ClO4)2·6H2O中的一种，所述路易斯碱选自TMG、DBN、DBU、BTMG、
Figure BDA0002874193000000061
中的一种。
在一种实施方式中，上述步骤一中，反应结束后，使用二氯甲烷稀释，再依次经硅藻土过滤，加入硅胶旋干，柱层析得到所述中间产物；
所述步骤二中，反应结束后，直接旋干，采用柱层析分离得到所述手性胺化合物。
在一种实施方式中，上述步骤一中反应在0℃条件下进行。
在一种实施方式中，上述步骤一中，以物质的量计，所述肉桂醇衍生酯的用量为x，所述甲胺化合物的用量为1.5x，所述钯催化剂用量以Pd元素计为0.1x，手性醛化合物用量为0.1～0.2x，路易斯酸用量为0.8x，路易斯碱用量为x。
本发明的目的之二在于提供一种上述手性胺化合物。其技术方案为：
一种手性胺化合物，其关键在于结构如前述式(Ⅰ)、(Ⅱ)或(Ⅲ)所示。
附图说明
图1为催化合成手性胺化合物的反应路线示意图以及使用的手性醛催化剂；
图2为以喹啉2-甲胺和一种肉桂醇衍生酯作为原料，催化合成手性胺化合物的反应路线图，及其使用的手性醛催化剂；
图3为分别以多种肉桂醇衍生酯作为原料，催化合成手性胺化合物的反应路线图，以及生成的手性胺化合物的分离效率、ee值；
图4为分别以多种甲胺化合物作为原料，催化合成手性胺化合物的反应路线图，以及生成的手性胺化合物的分离效率、ee值；
图5为分子结构中含氮杂环基团为β位取代基的甲胺化合物为原料，催化合成手性胺化合物的反应路线图。
具体实施方式
以下结合实施例和附图对本发明作进一步说明。
一种手性胺化合物的制备方法，其过程为：
步骤一、在N2保护气氛下，将钯催化剂和溶剂加入到干燥的反应容器中，搅拌溶解，再将甲胺化合物、肉桂醇衍生酯、手性醛化合物、反应助剂依次加入反应容器中，-40℃-80℃条件下反应，TCL检测反应进程，至肉桂醇衍生酯2消耗完，反应结束后，二氯甲烷稀释，硅藻土过滤，加入硅胶旋干，柱层析得到中间产物，紧接着进行步骤二；
步骤二、向所述中间产物中依次加入Boc2O、Na2CO3，室温下反应，TCL检测反应进程，待反应结束后，直接旋干，采用柱层析分离得到所述手性胺化合物。
溶剂可以是甲苯。钯催化剂可以是由[Pd(C3H5)Cl]2、Pd(OAc)2、Pd(PPh3)4、Pd(CH3CN)2Cl2中的一种与dppp组成，也可以是由[Pd(C3H5)Cl]2与dppf、dppb、PPh3、dppe中的一种组成。反应助剂为路易斯酸和路易斯碱，其中路易斯酸选自ZnF2、Zn(OAc)2、Zn(OTf)2、ZnBr2、ZnCl2、Zn(ClO4)2·6H2O中的一种，路易斯碱选自TMG、DBN、DBU、BTMG、
Figure BDA0002874193000000071
中的一种。
步骤一中，以物质的量计，记肉桂醇衍生酯的用量为x，甲胺化合物的用量超过肉桂醇衍生酯的用量，如1.5x，钯催化剂用量以Pd元素计为0.1x，手性醛化合物0.1～0.2x，路易斯酸用量为0.8x，路易斯酸用量为x。反应过程如图1所示。其中，R1或为六元含氮不饱和杂环基团，或为苯并六元含氮不饱和杂环基团，且R1为N原子的α位或β位取代基；R2选自H、取代或非取代的链烃基、取代或非取代的芳香基、取代或非取代的呋喃基、取代或非取代的噻吩基中的任意一种；R3为H或甲基。
手性醛化合物3可以是如图1中结构式3a～3j所示的化合物。
制备得到的手性胺化合物含有吡啶结构单元，这类含氮芳杂环结构在天然产物、医药、农药以及生物活性分子中广泛存在，因而手性胺化合物能够用于合成上述领域的手性化合物。
结合典型化合物进一步说明上述制备方法。
实施例1～10
在干燥的反应管中加入[Pd(C3H5)Cl]2(3.6mg,0.01mmol)、dppp(8.2mg,0.02mmol)，再加入0.5ml甲苯，氮气氛围下室温搅拌30分钟。在N2保护下，将喹啉2-甲胺1a(47.4mg,0.3mmol)、肉桂醇衍生酯2a(61.0mg,0.2mmol)、手性醛化合物3(0.02mmol)，ZnF2(16.5mg,0.16mmol)、TMG(25μL,0.2mmol)和甲苯(1.0mL)依次加入反应管中。反应在0℃条件下进行，TCL检测反应进程，直至化合物2a消失完，待反应结束后，二氯甲烷稀释，硅藻土过滤，加入硅胶旋干，柱层析得到中间产物，洗脱剂组成为二氯甲烷：甲醇：三乙胺＝150:2:5。将中间产物溶于DCM(1.5ml)中，紧接着依次加入Boc2O(0.15mmol)、Na2CO3(0.2mmol)，TCL检测反应进程，待反应结束后，直接旋干，柱层析得到产物4a。反应完成后，测定分离效率，通过手性HPLC测定产物ee值。
反应过程如图2所示，图中还给出了可以使用的不同的手性醛化合物。实施例1～10分别使用不同的手性醛化合物作为催化剂，保持其余条件不变，不同实施例的反应时间、分离效率和产物ee值如表1所示。可以看到，当使用手性醛化合物3e作为催化剂时，产物ee值高达94％。
表1使用不同手性醛化合物作为催化剂的实施例测得的反应数据
Figure BDA0002874193000000091
注：[c]产物ee值通过手性HPLC测定。[d]＝n.d.＝Not determined.
实施例11～34
考察不同的肉桂醇衍生酯2作为反应原料对反应的影响。
在干燥的反应管中加入[Pd(C3H5)Cl]2(3.6mg,0.01mmol)、dppp(8.2mg,0.02mmol)，再加入0.5ml甲苯，氮气氛围下室温搅拌30分钟。在N2保护下，将喹啉2-甲胺1a(47.4mg,0.3mmol)、肉桂醇衍生酯2(0.2mmol)、手性醛化合物3e(9.2mg,0.02mmol)，ZnF2(16.5mg,0.16mmol)、TMG(25μL,0.2mmol)和甲苯(1.0mL)依次加入反应管中。反应在0℃条件下进行，TCL检测反应进程，直至化合物2消失完，待反应结束后，二氯甲烷稀释，硅藻土过滤，加入硅胶旋干，柱层析得到中间产物。将中间产物溶于DCM(1.5ml)中，紧接着依次加入Boc2O(0.15mmol)、Na2CO3(0.2mmol)，TCL检测反应进程，待反应结束后，直接旋干，柱层析得到产物4。反应完成后，测定分离效率，通过手性HPLC测定产物ee值。
反应过程如图3所示，图中还给出了使用不同代表性肉桂醇衍生酯2生成的产物结构4a～4x。实施例11～34分别使用不同的肉桂醇衍生酯2，保持其余条件不变，不同实施例的肉桂醇衍生酯2结构、分离效率和产物ee值如表2所示。可以看到，在所列出的24个实施例中，产物ee值较大，最低为79％。
表2使用不同肉桂醇衍生酯作为反应物的实施例测得产物数据
Figure BDA0002874193000000101
Figure BDA0002874193000000111
Figure BDA0002874193000000121
实施例35～40
考察不同的甲胺化合物1作为反应原料对反应的影响。
在干燥的反应管中加入[Pd(C3H5)Cl]2(3.6mg,0.01mmol)、dppp(8.2mg,0.02mmol)，再加入0.5ml甲苯，氮气氛围下室温搅拌30分钟。在N2保护下，将甲胺化合物1(0.3mmol)、肉桂醇衍生酯2a(61.0mg,0.2mmol)、手性醛化合物3e(9.2mg,0.02mmol；或18.4mg，0.04mmol)，ZnF2(16.5mg,0.16mmol)、TMG(25μL,0.2mmol)和甲苯(1.0mL)依次加入反应管中。反应在0℃条件下进行，TCL检测反应进程，直至化合物2a消失完，待反应结束后，二氯甲烷稀释，硅藻土过滤，加入硅胶旋干，柱层析得到中间产物。将中间产物溶于DCM(1.5ml)中，紧接着依次加入Boc2O(0.15mmol)、Na2CO3(0.2mmol)，TCL检测反应进程，待反应结束后，直接旋干，柱层析得到产物5。反应完成后，测定分离效率，通过手性HPLC测定产物ee值。
反应过程如图4所示，图中还给出了使用不同甲胺化合物1生成的产物结构5a～5f。实施例35～40使用不同的甲胺化合物1，保持其余条件不变或增加手性醛化合物的用量(实施例36、39、40、42)，不同实施例的甲胺化合物1结构、分离效率和产物ee值如表3所示。从不同甲胺化合物1出发，产物的分离效率和ee值有较大差别。对比实施例35与36、41与42可以看出，仅将手性醛化合物相对肉桂醇衍生酯2a的用量由10mol％增加至20mol％，保持其余条件不变，产物分离效率提高，但产物ee值均有所降低。
表3使用不同甲胺化合物作为反应物的实施例测得产物数据
Figure BDA0002874193000000131
注：[a]手性醛化合物的用量为0.04mmol。其余各实施例均为0.02mmol。
实施例41～42
当甲胺化合物中六元含氮不饱和杂环基团或苯并六元含氮不饱和杂环基团为N原子的β位取代基时，考察其对反应的影响。
使用等量的喹啉3-甲胺1’a(实施例41)或异喹啉4-甲胺1’b实施例42)替换喹啉2-甲胺1a，其余与实施例11的反应条件相同，进行反应，得到产物4’a和4’b。反应过程如图5所示。反应完成后，测定分离效率，发现分离效率分别为18％和15％，远低于实施例11的77％。实施例41、42与实施例11的对比表明，甲胺化合物中六元含氮不饱和杂环基团或苯并六元含氮不饱和杂环基团为N原子的β位取代基时，其反应效率较α位取代基的情形低。
与现有技术相比，本发明的有益效果：本方法工艺路线简单，反应条件温和，无外加保护基的条件下就能直接合成手性胺类化合物。
实施例11～40的产物表征数据如下：
Figure BDA0002874193000000141
90/10,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)7.604min,tR(minor)6.934min；[a]D 20＝+18.01(c＝0.65CHCl3)；1H NMR(600MHz,CDCl3)δ8.10–8.05(m,2H),7.78(d,J＝8.0Hz,1H),7.69(t,J＝7.6Hz,1H),7.51(t,J＝7.4Hz,1H),7.33(d,J＝8.4Hz,1H),7.25(d,J＝5.5Hz,4H),7.17(d,J＝6.1Hz,1H),6.39(d,J＝15.7Hz,1H),6.15(d,J＝6.1Hz,1H),6.13–6.06(m,1H),5.08(d,J＝6.0Hz,1H),2.85(dd,J＝6.0,6.0Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.07,155.49,147.60,136.49,133.10,129.56,129.19,128.44,127.61,127.38,127.15,126.30,126.17,125.60,125.06,120.06,79.37,55.65,40.20,28.46；HRMS(ESI):calcd.for C24H27N2O2(M+H)+:375.2067,found:375.2067.
Figure BDA0002874193000000142
mL/min,T＝30℃),UV 250nm,tR(major)16.959min,tR(minor)14.609min；[a]D 20＝+1.16(c＝0.46,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(m,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.4Hz,1H),7.51(t,J＝7.3Hz,1H),7.40(d,J＝7.5Hz,1H),7.36(d,J＝8.3Hz,1H),7.30–7.24(m,1H),7.12(m,2H),6.74(d,J＝15.7Hz,1H),6.19(d,J＝6.1Hz,1H),6.15–6.05(m,1H),5.11(d,J＝6.2Hz,1H),2.89(dd,J＝6.0,6.0Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ159.84,155.50,147.56,136.61,135.60,132.63,129.59,129.47,129.32,129.17,128.74,128.15,127.61,127.39,126.99,126.72,126.33,120.01,79.40,55.41,40.39,28.44；HRMS(ESI):calcd.for C24H26ClN2O2(M+H)+:409.1677,found:409.1673.
Figure BDA0002874193000000151
79％,Daicel Chirapak IA-H column(hexane/isopropanol＝70/30,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)5.104min,tR(minor)14.714min；[a]D 20＝-2.57(c＝0.44,CHCl3)；1H NMR(600MHz,CDCl3)δ8.01(m,2H),7.71(d,J＝8.0Hz,1H),7.62(t,J＝7.6Hz,1H),7.43(t,J＝7.4Hz,1H),7.38(d,J＝7.9Hz,1H),7.29(m,2H),7.09(t,J＝7.4Hz,1H),6.99–6.89(m,1H),6.60(d,J＝15.6Hz,1H),6.10(d,J＝5.7Hz,1H),6.02–5.93(m,1H),5.03(d,J＝5.6Hz,1H),2.80(dd,J＝6.0,6.0Hz,2H),1.37(s,9H)；13C NMR(151MHz,CDCl3)δ158.70,154.32,146.42,136.25,135.44,131.53,130.77,128.40,128.02,127.75,127.24,126.42,126.23,126.18,126.07,125.15,122.00,118.84,78.22,54.23,39.08,27.29；HRMS(ESI):calcd.for C24H26BrN2O2(M+H)+:453.1172,found:453.1172.
Figure BDA0002874193000000152
rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)15.548min,tR(minor)13.064min；[a]D 20＝+3.14(c＝0.29,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(m,2H),7.80(d,J＝8.0Hz,1H),7.70(t,J＝7.2Hz,1H),7.52(t,J＝7.2Hz,1H),7.36(d,J＝8.4Hz,1H),7.31–7.27(m,1H),7.09(m,3H),6.54(d,J＝18.0Hz,1H),6.17(d,J＝6.1Hz,1H),6.00–5.86(m,1H),5.09(d,J＝6.2Hz,1H),2.88(dd,J＝6.0,6.0Hz,2H),2.19(s 3H),1.46(s,9H)；13C NMR(151MHz,CDCl3)δ160.02,155.46,147.57,136.64,136.46,135.04,131.20,130.05,129.55,129.18,127.58,127.37,127.08,126.87,126.30,125.97,125.80,120.14,79.36,55.59,40.30,28.46,19.68；HRMS(ESI):calcd.for C25H29N2O2(M+H)+:389.2224,found:389.2222.
Figure BDA0002874193000000153
flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)13.869min,tR(minor)12.908min；[a]D 20＝+17.78(c＝0.49,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(m,2H),7.80(d,J＝8.0Hz,1H),7.71(t,J＝7.3Hz,1H),7.52(t,J＝7.3Hz,1H),7.33(d,J＝8.4Hz,1H),7.23(s,1H),7.19–7.07(m,3H),6.32(d,J＝15.8Hz,1H),6.17(d,J＝6.9Hz,1H),6.12(m,1H),5.09(d,J＝6.3Hz,1H),2.95–2.74(m,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ159.80,155.47,147.57,139.34,136.60,134.40,131.70,129.63,129.17,129.03,127.61,127.57,127.38,127.05,126.37,126.10,124.36,119.99,79.44,55.48,40.20,28.44；HRMS(ESI):calcd.for C24H26ClN2O2(M+H)+:409.1677,found:409.1676.
Figure BDA0002874193000000161
rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)13.869min,tR(minor)12.908min；[a]D 20＝+25.63(c＝0.24,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(t,J＝8.0Hz,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.4Hz,1H),7.51(t,J＝7.3Hz,1H),7.34(d,J＝8.4Hz,1H),7.14(t,J＝7.5Hz,1H),7.09–7.04(m,2H),6.99(d,J＝7.2Hz,1H),6.36(d,J＝15.7Hz,1H),6.16–6.04(m,2H),5.08(d,J＝5.2Hz,1H),2.92–2.76(m,2H),2.29(s,3H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.16,155.49,147.61,137.95,137.39,136.47,133.21,129.53,129.19,128.33,127.94,127.59,127.38,126.90,126.27,125.35,123.33,120.05,79.37,55.68,40.18,28.45,21.33；HRMS(ESI):calcd.for C25H29N2O2(M+H)+:389.2224,found:389.2221.
Figure BDA0002874193000000162
(hexane/isopropanol＝90/0,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)12.945min,tR(minor)11.742min；[a]D 20＝+23.58(c＝0.51,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(t,J＝8.7Hz,2H),7.78(d,J＝7.9Hz,1H),7.73–7.66(m,1H),7.51(t,J＝7.2Hz,1H),7.33(d,J＝8.4Hz,1H),7.16(t,J＝7.9Hz,1H),6.86(d,J＝7.5Hz,1H),6.79(s,1H),6.75–6.70(m,1H),6.36(d,J＝15.7Hz,1H),6.15(d,J＝6.2Hz,1H),6.13–6.06(m,1H),5.08(d,J＝6.0Hz,1H),3.76(s,3H),2.95–2.77(m,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.05,159.78,155.48,147.60,138.93,136.49,133.00,129.55,129.39,129.18,127.60,127.38,126.29,125.97,120.05,118.86,112.83,111.58,79.37,55.64,55.17,40.14,28.45；HRMS(ESI):calcd.for C25H29N2O3(M+H)+:405.2173,found:405.2170.
Figure BDA0002874193000000171
1.0mL/min,T＝30℃),UV 254nm,tR(major)13.365min,tR(minor)12.591min；[a]D 20＝+39.60(c＝0.28,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(t,J＝8.2Hz,2H),7.79(d,J＝7.9Hz,1H),7.70(t,J＝7.3Hz,1H),7.51(t,J＝7.3Hz,1H),7.34(d,J＝8.2Hz,1H),7.15(d,J＝7.5Hz,2H),7.06(d,J＝7.5Hz,2H),6.36(d,J＝15.7Hz,1H),6.13(d,J＝5.3Hz,1H),6.08–5.97(m,1H),5.06(d,J＝5.8Hz,1H),2.83(d,J＝6.7Hz,2H),2.30(s,3H),1.45(s,9H)；13CNMR(150MHz,CDCl3)δ160.18,155.48,147.61,136.89,136.42,134.67,132.98,129.51,129.20,129.13,127.58,127.37,126.26,126.07,124.49,120.07,79.34,55.72,40.16,28.45,21.11；HRMS(ESI):calcd.for C25H29N2O2(M+H)+:389.2224,found:389.2223.
Figure BDA0002874193000000172
(hexane/isopropanol＝90/10,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)12.904min,tR(minor)12.091min；[a]D 20＝+28.16(c＝0.43,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(t,J＝8.0Hz,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.4Hz,1H),7.51(t,J＝7.4Hz,1H),7.34(d,J＝8.4Hz,1H),7.19(d,J＝8.4Hz,2H),6.79(d,J＝8.5Hz,2H),6.33(d,J＝15.7Hz,1H),6.13(d,J＝6.3Hz,1H),6.00–5.89(m,1H),5.06(d,J＝6.0Hz,1H),3.77(s,3H),2.88–2.77(m,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.22,158.95,155.49,147.61,136.41,132.48,130.32,129.51,129.19,127.59,127.36,127.27,126.25,123.33,120.07,113.90,79.32,55.76,55.27,40.19,28.45；HRMS(ESI):calcd.for C25H29N2O3(M+H)+:405.2173,found:405.2175.
Figure BDA0002874193000000173
(hexane/isopropanol＝90/10,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)7.879min,tR(minor)7.381min；[a]D 20＝+6.60(c＝0.32,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(m,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.2Hz,1H),7.52(t,J＝7.2Hz,1H),7.34(d,J＝8.3Hz,1H),7.21(dd,J＝7.8,5.7Hz,2H),6.93(t,J＝8.5Hz,2H),6.34(d,J＝15.7Hz,1H),6.15(d,J＝5.7Hz,1H),6.06–5.97(m,1H),5.08(d,J＝5.9Hz,1H),2.83(dd,J＝6.0,6.0Hz,2H),1.44(s,9H)；13C NMR(151MHz,CDCl3)δ162.90,161.27,159.99,155.48,147.59,136.52,131.80,129.58,129.17,127.61,127.59,127.56,127.37,126.32,125.45,120.02,115.34,115.20,79.38,55.59,40.21,28.43；HRMS(ESI):calcd.forC24H26FN2O2(M+H)+:393.1973,found:393.1974.
Figure BDA0002874193000000181
(hexane/isopropanol＝98/2,flow rate 0.8mL/min,T＝30℃),UV 254nm,tR(major)29.603min,tR(minor)27.984min；[a]D 20＝+18.93(c＝0.30,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(dd,J＝19.9,8.3Hz,2H),7.80(d,J＝8.0Hz,1H),7.71(t,J＝7.5Hz,1H),7.52(t,J＝7.4Hz,1H),7.35(dd,J＝17.6,8.2Hz,3H),7.11(d,J＝8.0Hz,2H),6.32(d,J＝15.8Hz,1H),6.15(d,J＝6.0Hz,1H),6.14–6.06(m,1H),5.08(d,J＝5.9Hz,1H),2.83(dd,J＝6.0.6.0Hz,2H),1.44(s,9H)；13C NMR(150MHz,CDCl3)δ159.87,155.47,147.58,136.55,136.40,131.81,131.51,129.61,129.17,127.68,127.60,127.37,126.66,126.36,120.82,120.01,79.41,55.49,40.27,28.44；HRMS(ESI):calcd.for C24H26BrN2O2(M+H)+:453.1172,found:453.1168.
Figure BDA0002874193000000182
(hexane/isopropanol＝98/2,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)20.283min,tR(minor)18.948min；[a]D 20＝+21.34(c＝0.46,CHCl3)；1HNMR(600MHz,CDCl3)δ8.09(dd,J＝17.4,8.4Hz,2H),7.79(d,J＝8.0Hz,1H),7.71(t,J＝7.3Hz,1H),7.52(t,J＝7.4Hz,1H),7.33(d,J＝8.3Hz,1H),7.19(dd,J＝21.2,8.3Hz,4H),6.33(d,J＝15.7Hz,1H),6.17(d,J＝6.8Hz,1H),6.13–6.03(m,1H),5.08(d,J＝6.4Hz,1H),2.83(dd,J＝6.0,6.0Hz,2H),1.44(s,9H)；13C NMR(151MHz,CDCl3)δ159.88,155.48,147.57,136.57,135.94,132.71,131.77,129.62,129.15,128.56,127.61,127.35,126.49,126.36,120.01,79.42,55.52,40.26,28.44；HRMS(ESI):calcd.for C24H26ClN2O2(M+H)+:409.1677,found:409.1676.
Figure BDA0002874193000000183
column(hexane/isopropanol＝94/6,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)8.925min,tR(minor)8.298min；[a]D 20＝+26.90(c＝0.51,CHCl3)；1H NMR(600MHz,CDCl3)δ8.12–8.03(m,2H),7.78(d,J＝8.0Hz,1H),7.69(t,J＝7.6Hz,1H),7.51(t,J＝7.5Hz,1H),7.33(d,J＝8.4Hz,1H),7.05–6.97(m,3H),6.33(d,J＝15.7Hz,1H),6.12(d,J＝5.6Hz,1H),6.07–5.99(m,1H),5.06(d,J＝5.7Hz,1H),2.83(d,J＝5.8Hz,2H),2.20(s,6H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.23,155.48,147.61,136.47,136.41,135.60,135.11,133.09,129.72,129.50,129.20,127.59,127.46,127.37,126.24,124.29,123.63,120.07,79.34,55.74,40.15,28.46,19.69,19.42；HRMS(ESI):calcd.for C26H31N2O2(M+H)+:403.2380,found:403.2378.
Figure BDA0002874193000000191
(hexane/isopropanol＝70/30,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)6.921min,tR(minor)6.135min；[a]D 20＝+28.78(c＝0.36,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(dd,J＝6.0,6.0Hz,2H),7.80(d,J＝7.9Hz,1H),7.71(t,J＝7.4Hz,1H),7.52(t,J＝7.3Hz,1H),7.35(d,J＝8.1Hz,1H),6.79(m,3H),6.33(d,J＝15.6Hz,1H),6.14(d,J＝5.3Hz,1H),6.08–5.90(m,1H),5.07(d,J＝5.3Hz,1H),3.85(m,6H),2.82(d,J＝18Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.17,155.46,149.00,148.55,147.58,136.47,132.68,130.67,129.54,129.14,127.60,127.37,126.29,123.74,120.07,119.12,111.20,108.90,79.34,55.94,55.81,40.25,28.44；HRMS(ESI):calcd.for C26H31N2O4(M+H)+:435.2278,found:435.2279.
Figure BDA0002874193000000192
flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)18.350min,tR(minor)17.383min；[a]D 20＝+29.31(c＝0.31,CHCl3)；1H NMR(600MHz,CDCl3)δ8.09(dd,J＝13.8,8.5Hz,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.3Hz,1H),7.52(t,J＝7.3Hz,1H),7.33(d,J＝8.2Hz,1H),6.80(s,1H),6.69(s,2H),6.29(d,J＝15.6Hz,1H),6.13(d,J＝5.6Hz,1H),5.96–5.86(m,3H),5.05(d,J＝5.9Hz,1H),2.82(dd,J＝15.7,8.5Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.09,155.47,147.89,147.58,146.85,136.47,132.62,131.99,129.55,129.16,127.59,127.36,126.29,123.80,120.57,120.05,108.16,105.61,100.93,79.36,55.69,40.08,28.44；HRMS(ESI):calcd.for C25H27N2O4(M+H)+:419.1965,found:419.1965.
Figure BDA0002874193000000201
＝92/8,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)11.698min,tR(minor)10.971min；[a]D 20＝+32.40(c＝0.40,CHCl3)；1H NMR(600MHz,CDCl3)δ8.01(m,2H),7.72(d,J＝8.0Hz,1H),7.63(t,J＝6.0Hz,1H),7.44(t,J＝7.4Hz,1H),7.26(d,J＝8.4Hz,1H),6.93(d,J＝12.1Hz,1H),6.85(d,J＝8.3Hz,1H),6.75(t,J＝8.5Hz,1H),6.20(d,J＝15.7Hz,1H),6.06(d,J＝5.3Hz,1H),5.97–5.83(m,1H),4.98(d,J＝5.7Hz,1H),3.77(s,3H),2.74(dd,J＝6.0,6.0Hz,2H),1.37(s,9H)；13C NMR(151MHz,CDCl3)δ159.98,155.47,153.32,151.69,147.58,136.51,131.55,129.58,129.16,127.59,127.37,126.32,124.94,122.25,120.02,113.39,113.34,113.22,79.38,56.34,55.61,40.11,28.43；HRMS(ESI):calcd.forC25H28FN2O3(M+H)+:423.2078,found:423.2079.
Figure BDA0002874193000000202
98/2,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)15.173min,tR(minor)13.719min；[a]D 20＝-16.13(c＝0.56,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(d,J＝8.4Hz,2H),7.79(d,J＝8.0Hz,1H),7.71(m,1H),7.51(t,J＝7.4Hz,1H),7.33(d,J＝8.4Hz,1H),7.28(t,J＝7.5Hz,2H),7.16(m,3H),6.16(s,1H),6.06(d,J＝5.9Hz,1H),5.16(d,J＝6.7Hz,1H),2.72(d,J＝6.4Hz,2H),1.92(d,J＝0.9Hz,3H),1.43(s,9H)；13C NMR(151MHz,CDCl3)δ160.72,155.47,147.69,138.13,136.27,134.82,129.51,129.14,128.81,128.59,127.97,127.60,127.38,126.23,126.10,120.25,79.28,54.60,48.42,28.45,18.14；HRMS(ESI):calcd.for C25H29N2O2(M+H)+:389.2224,found:389.2223.
Figure BDA0002874193000000203
90/10,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)10.130min,tR(minor)12.696min；[a]D 20＝+37.68(c＝0.62,CHCl3)；1HNMR(600MHz,CDCl3)δ8.09(d,J＝8.0Hz,2H),7.81–7.69(m,5H),7.60(s,1H),7.54–7.46(m,2H),7.44–7.34(m,3H),6.54(d,J＝15.7Hz,1H),6.27–6.21(m,1H),6.19(d,J＝6.3Hz,1H),5.12(d,J＝6.0Hz,1H),2.90(dd,J＝6.0,6.0Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ160.09,155.54,147.62,136.53,134.92,133.63,133.18,132.83,129.59,129.20,128.04,127.90,127.63,127.40,126.32,126.15,125.72,125.63,123.68,120.09,79.41,55.68,40.42,28.47；HRMS(ESI):calcd.for C28H29N2O2(M+H)+:425.2224,found:425.2224.
Figure BDA0002874193000000211
94/6,flow rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)11.410min,tR(minor)9.897min；[a]D 20＝+24.20(c＝0.10,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(m,2H),7.79(d,J＝8.0Hz,1H),7.69(t,J＝7.2Hz,1H),7.51(t,J＝7.3Hz,1H),7.34(d,J＝8.4Hz,1H),δ7.25(s,1H),6.30(s,1H),6.20(d,J＝15.7Hz,1H),6.12(s,1H),6.09(s,1H),6.06–5.99(m,1H),5.06(d,J＝6.2Hz,1H),2.92–2.75(m,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ159.96,155.45,152.86,147.58,141.50,136.51,129.52,129.19,127.58,127.37,126.28,124.33,121.62,120.03,111.05,106.71,79.37,55.57,39.85,28.42；HRMS(ESI):calcd.forC22H25N2O3(M+H)+:365.1860,found:365.1858.
Figure BDA0002874193000000212
rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)11.027min,tR(minor)9.895min；[a]D 20＝+36.06(c＝0.47,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(m,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.5Hz,1H),7.51(t,J＝7.4Hz,1H),7.33(d,J＝8.4Hz,1H),7.06(d,J＝4.7Hz,1H),6.92–6.86(m,1H),6.82(s,1H),6.50(d,J＝15.5Hz,1H),6.14(d,J＝5.8Hz,1H),5.99–5.90(m,1H),5.05(d,J＝6.0Hz,1H),2.81(d,J＝6.4Hz,2H),1.45(s,9H)；13C NMR(151MHz,CDCl3)δ159.92,155.45,147.60,142.57,136.50,129.55,129.19,127.59,127.38,127.18,126.30,126.16,125.44,124.71,123.60,120.06,79.40,55.59,40.01,28.44；HRMS(ESI):calcd.for C22H25NO2S(M+H)+:381.1631,found:381.1629.
Figure BDA0002874193000000213
mL/min,T＝30℃),UV 254nm,tR(major)7.856min,tR(minor)6.995min；[a]D 20＝-43.99(c＝0.32,CHCl3)；1H NMR(600MHz,CDCl3)δ8.10(d,J＝8.4Hz,1H),8.06(d,J＝8.4Hz,1H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.6Hz,1H),7.51(t,J＝7.5Hz,1H),7.33(d,J＝8.4Hz,1H),6.07(s,1H),5.71(m,1H),5.03(m,3H),2.78–2.62(m,2H),1.47(s,9H)；13C NMR(151MHz,CDCl3)δ160.13,155.47,147.53,136.42,133.77,129.50,129.16,127.56,126.24,120.03,118.07,79.30,55.29,40.77,29.70,28.44；HRMS(ESI):calcd.for C18H23N2O2(M+H)+:299.1754,found:299.1751.
Figure BDA0002874193000000221
1.0mL/min,T＝30℃),UV 254nm,tR(major)5.826min,tR(minor)5.374min；[a]D 20＝-32.96(c＝0.18,CHCl3)；1H NMR(600MHz,CDCl3)δ8.08(m,2H),7.79(d,J＝8.0Hz,1H),7.70(t,J＝7.3Hz,1H),7.51(t,J＝7.4Hz,1H),7.32(d,J＝8.2Hz,1H),6.00(s,1H),5.44(m,1H),5.36–5.27(m,1H),4.94(d,J＝6.0Hz,1H),2.68–2.54(m,2H),1.59(d,J＝5.1Hz,3H),1.46(s,9H)；13C NMR(151MHz,CDCl3)δ160.57,155.47,147.56,136.27,129.42,129.15,128.69,127.54,127.31,126.24,126.15,120.06,79.22,55.67,39.68,28.44,17.93；HRMS(ESI):calcd.for C19H25N2O2(M+H)+:313.1911,found:313.1907.
Figure BDA0002874193000000222
rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)6.381min,tR(minor)5.882min；[a]D 20＝-21.57(c＝0.27,CHCl3)；1H NMR(600MHz,CDCl3)δ8.00(dd,J＝16.1,8.2Hz,2H),7.71(d,J＝7.8Hz,1H),7.62(t,J＝7.3Hz,1H),7.43(t,J＝6.9Hz,1H),7.24(d,J＝7.6Hz,1H),5.96(s,1H),5.32(d,J＝6.0Hz,1H),5.22(dd,J＝14.2,6.9Hz,1H),4.87(s,1H),2.55(d,J＝27.8Hz,2H),1.82(d,J＝5.1Hz,2H),1.39(s,9H),1.22–1.17(m,2H),0.72(d,J＝5.9Hz,3H)；13C NMR(151MHz,CDCl3)δ160.51,155.45,147.55,136.24,134.24,129.41,129.14,127.53,127.31,126.14,125.06,120.12,79.19,55.69,39.65,34.59,28.46,22.42,13.50；HRMS(ESI):calcd.forC21H29N2O2(M+H)+:341.2224,found:341.2222.
Figure BDA0002874193000000223
rate 1.0mL/min,T＝30℃),UV 250nm,tR(major)9.194min,tR(minor)8.465min；[a]D 20＝+46.37(c＝0.34,CHCl3)；1H NMR(600MHz,CDCl3)δ8.13(d,J＝8.4Hz,1H),8.08(d,J＝8.4Hz,1H),7.80(d,J＝8.0Hz,1H),7.71(t,J＝7.7Hz,1H),7.53(t,J＝7.5Hz,1H),7.36(dd,J＝15.2,6.1Hz,3H),7.30–7.24(m,3H),6.22–6.05(m,2H),5.69(d,J＝15.7Hz,1H),5.06(d,J＝6.2Hz,1H),2.94–2.73(m,2H),1.48(s,9H)；13CNMR(151MHz,CDCl3)δ159.49,155.43,147.54,139.28,136.69,131.45,129.62,129.20,128.23,127.99,127.60,127.40,126.40,123.42,119.97,112.92,88.65,87.94,79.52,55.10,39.99,28.46.；HRMS(ESI):calcd.forC26H27N2O2(M+H)+:399.2067,found:399.2063.
Figure BDA0002874193000000231
90/10,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)11.524min,tR(minor)9.498min；[a]D 20＝-21.73(c＝0.36,CHCl3)；1H NMR(600MHz,CDCl3)δ8.39(d,J＝8.7Hz,1H),7.99(d,J＝9.2Hz,1H),7.42(d,J＝9.2Hz,1H),7.33(d,J＝8.7Hz,1H),7.18(d,J＝3.7Hz,4H),7.12–7.09(m,1H),6.32(d,J＝12Hz,1H),6.04–5.97(m,1H),5.95(d,J＝6.1Hz,1H),5.01(d,J＝5.9Hz,1H),3.98(s,3H),2.77(dd,J＝6.0,6.0Hz,2H),1.37(s,9H)；13C NMR(151MHz,CDCl3)δ158.65,155.46,153.91,143.64,137.34,135.06,133.23,129.92,128.45,127.79,127.20,126.16,125.34,121.31,116.61,107.56,79.47,57.14,55.33,40.00,28.43；HRMS(ESI):calcd.for C25H28BrN2O3(M+H)+:483.1278,found:483.1276.
Figure BDA0002874193000000232
30℃),UV 254nm,tR(major)6.265min,tR(minor)5.703min；[a]D 20＝-4.03(c＝0.09,CHCl3)；1H NMR(600MHz,CDCl3)δ8.55(d,J＝4.3Hz,1H),7.61(t,J＝7.3Hz,1H),7.24(dd,J＝4.7,2.8Hz,4H),7.22–7.14(m,3H),6.34(d,J＝15.7Hz,1H),6.07–5.99(m,1H),5.69(s,1H),4.87(d,J＝6.4Hz,1H),2.71(d,J＝6.0Hz,2H),1.39(s,9H)；13C NMR(151MHz,CDCl3)δ159.86,155.22,148.91,137.09,136.06,132.67,128.07,126.79,125.78,125.24,121.89,121.51,79.06,54.92,39.80,28.02；HRMS(ESI):calcd.for C20H25N2O2(M+H)+:325.1911,found:325.1912.
Figure BDA0002874193000000233
mL/min,T＝30℃),UV 254nm,tR(major)7.964min,tR(minor)7.353min；[a]D 20＝-2.57(c＝0.44,CHCl3)；1H NMR(600MHz,CDCl3)δ8.62(d,J＝6.0Hz,1H),7.75(d,J＝8.2Hz,1H),7.29–7.25(m,4H),7.20(m,1H),7.13(d,J＝8.3Hz,1H),6.38(d,J＝15.8Hz,1H),6.08–5.98(m,1H),5.54(s,1H),4.85(s,1H),2.71(t,J＝6.0Hz,2H),1.41(s,9H)；13C NMR(150MHz,CDCl3)δ158.88,155.27,150.40,138.98,137.21,133.41,128.48,127.31,126.16,125.08,123.08,119.12,79.60,54.91,39.80,28.36；HRMS(ESI):calcd.for C20H24BrN2O2(M+H)+:403.1016,found:403.1013.
Figure BDA0002874193000000241
90/10,flow rate 1.0mL/min,T＝30℃),UV 254nm,tR(major)6.695min,tR(minor)5.967min；[a]D 20＝+7.76(c＝0.26,CHCl3)；1H NMR(600MHz,CDCl3)δ7.59(t,J＝7.4Hz,1H),7.27(d,J＝15.0Hz,4H),7.21(d,J＝7.9Hz,2H),7.15(d,J＝7.3Hz,1H),6.39(d,J＝15.7Hz,1H),6.11–5.95(m,1H),5.50(d,J＝6.0Hz,1H),4.86(d,J＝6.4Hz,1H),2.72(s,2H),1.41(s,9H)；13C NMR(151MHz,CDCl3)δ161.39,155.36,151.30,139.15,137.32,133.48,128.57,127.39,126.26,125.22,123.00,120.36,79.75,55.13,39.90,28.44；HRMS(ESI):calcd.for C20H24ClN2O2(M+H)+:359.1521,found:359.1520.
Figure BDA0002874193000000242
mL/min,T＝30℃),UV 254nm,tR(major)7.938min,tR(minor)6.123min:[a]D 20＝-4.85(c＝0.36,CHCl3)；1H NMR(600MHz,CDCl3)δ7.69(d,J＝7.8Hz,1H),7.27(dd,J＝15.1,5.2Hz,4H),7.24–7.19(m,1H),7.14(d,J＝7.9Hz,1H),6.41(d,J＝15.7Hz,1H),6.09–5.99(m,1H),5.41(d,J＝6.7Hz,1H),4.85(d,J＝6.6Hz,1H),2.71(t,J＝6.4Hz,2H),1.41(s,9H)；13C NMR(151MHz,CDCl3)δ159.12,155.02,148.53,138.84,136.84,133.47,128.70,128.33,127.24,125.99,124.53,121.13,79.67,54.46,39.31,28.15；HRMS(ESI):calcd.forC20H23Cl2N2O2(M+H)+:393.1131,found:393.1131.
Figure BDA0002874193000000243
＝30℃),UV 254nm,tR(major)15.964min,tR(minor)13.174min；[a]D 20＝-12.20(c＝0.28,CHCl3)；1H NMR(600MHz,CDCl3)δ8.57(s,1H),8.54(s,1H),8.48(d,J＝2.3Hz,1H),7.29–7.26(m,4H),7.20(m,1H),6.39(d,J＝15.8Hz,1H),6.10–6.00(m,1H),5.51(s,1H),5.00(d,J＝5.6Hz,1H),2.76(t,J＝6.1Hz,2H),1.42(s,9H)；13C NMR(151MHz,CDCl3)δ155.92,155.25,143.97,143.58,143.49,137.02,133.79,128.50,127.43,126.19,124.54,79.85,53.26,39.64,28.33；HRMS(ESI):calcd.for C19H24N3O2(M+H)+:326.1863,found:326.1860.
最后需要说明的是，上述描述仅仅为本发明的优选实施例，本领域的普通技术人员在本发明的启示下，在不违背本发明宗旨及权利要求的前提下，可以做出多种类似的表示，这样的变换均落入本发明的保护范围之内。

Claims (7)

1.一种手性胺化合物的催化合成方法，其特征在于：在钯催化剂和一种手性醛化合物的催化作用下，甲胺化合物和肉桂醇衍生酯于碱性条件下反应生成中间产物，该中间产物再与Boc2O反应生成所述手性胺化合物；
所述甲胺化合物的结构为
Figure FDA0003673613100000011
R1或为以下基团中的一种
Figure FDA0003673613100000012
或为六元含氮不饱和杂环基团，或为苯并六元含氮不饱和杂环基团，且R1为N原子的α位或β位取代基；
所述肉桂醇衍生酯的结构为；
Figure FDA0003673613100000013
其中PG为4-CF3C6H4CO，R2选自H、取代或非取代的链烃基、取代或非取代的芳香基、取代或非取代的呋喃基、取代或非取代的噻吩基中的任意一种，R3为H或甲基；
所述手性胺化合物的结构如式(Ⅰ)：
Figure FDA0003673613100000014
具体步骤为：
步骤一、在保护气氛下，将钯催化剂和溶剂加入到干燥的反应容器中，搅拌溶解，再将所述甲胺化合物、肉桂醇衍生酯、手性醛化合物、反应助剂依次加入反应容器中，-40℃-80℃条件下反应，至肉桂醇衍生酯消耗完，反应结束后，分离得到中间产物，紧接着进行步骤二；
步骤二、向所述中间产物中依次加入Boc2O、Na2CO3，待反应结束后，分离得到所述手性胺化合物；
所述手性醛化合物或为
Figure FDA0003673613100000021
其中R5为H、TMS、4-FC6H4、4-MeOC6H4、4-CF3C6H4、3,5-2MeC6H3、3,5-2CF3C6H3中的一种，
或为
Figure FDA0003673613100000022
或为
Figure FDA0003673613100000023
或为
Figure FDA0003673613100000031
所述反应助剂为路易斯酸和路易斯碱，其中所述路易斯酸选自ZnF2、Zn(OAc)2、Zn(OTf)2、ZnBr2、ZnCl2、Zn(ClO4)2·6H2O中的一种，所述路易斯碱为TMG；
所述钯催化剂或由[Pd(C3H5)Cl]2、Pd(OAc)2、Pd(PPh3)4、Pd(CH3CN)2Cl2中的一种与dppp组成，或由[Pd(C3H5)Cl]2与dppf、dppb、PPh3、dppe中的一种组成。
2.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述手性胺化合物的结构如式(Ⅱ)：
Figure FDA0003673613100000032
其中R3为H或甲基；
R2为H、-CH3、-CH2CH2CH3，或选自如下基团中的一种：
Figure FDA0003673613100000041
3.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述手性胺化合物的结构如式(Ⅲ)：
Figure FDA0003673613100000051
其中R1选自以下基团中的任意一种：
Figure FDA0003673613100000052
4.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述溶剂为甲苯。
5.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述步骤一中，反应结束后，使用二氯甲烷稀释，再依次经硅藻土过滤，加入硅胶旋干，柱层析得到所述中间产物；
所述步骤二中，反应结束后，直接旋干，采用柱层析分离得到所述手性胺化合物。
6.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述步骤一中反应在0℃条件下进行。
7.根据权利要求1所述的一种手性胺化合物的催化合成方法，其特征在于：所述步骤一中，以物质的量计，所述肉桂醇衍生酯的用量为x，所述甲胺化合物的用量为1.5x，所述钯催化剂用量以Pd元素计为0.1x，手性醛化合物用量为0.1～0.2x，路易斯酸用量为0.8x，路易斯碱用量为x。
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