CN111004114B - 一种合成远程氟代芳基烯烃的方法 - Google Patents

一种合成远程氟代芳基烯烃的方法 Download PDF

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CN111004114B
CN111004114B CN201911374058.1A CN201911374058A CN111004114B CN 111004114 B CN111004114 B CN 111004114B CN 201911374058 A CN201911374058 A CN 201911374058A CN 111004114 B CN111004114 B CN 111004114B
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李立新
赵争光
罗浩天
李勇
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Xinyang Normal University
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Abstract

本发明公开了一种合成远程氟代芳基烯烃的方法，属于有机化学领域。以2‑烯丙基‑2‑苯乙基丙二酸二乙酯及其衍生物为原料，在磷配体、无机碱以及有机溶剂存在下反应，得到本发明所述氟代烯烃类化合物三乙基(E)‑1,1‑二氟‑7‑苯基庚‑6‑烯‑1,5,5‑三羧酸。本发明方法采用钯催化一步即可完成，将烯烃异构化的同时，实现二氟烷基化，为该类化合物合成提供了直接有效的途径。

Description

一种合成远程氟代芳基烯烃的方法
技术领域
本发明属于有机化学技术领域，涉及烯烃的氟烷基化的方法，具体涉及提供了一种合成远程氟代芳基烯烃的方法。
背景技术
含氟官能团在药物化学和生物化学中有着深远的影响，含氟基团可以改变分子在身体中吸收、分布代谢和排泄等特性。含氟烯烃化合物由于其具有广泛的转化特性，可以通过烯烃的双官能团化，引入不同的官能团，例如苯基，羟基、氨基、氰基等，进一步实现含氟化合物的转化和应用，为药物分子活性研究提供了有力的工具。
传统上，氟代烯烃的合成多依赖于过渡金属催化，反应过程需要大量的氧化剂促使金属催化剂的循环，抑或需要昂贵的三氟甲基化试剂，因此严重阻碍了氟代烯烃化合物的研究和制备。到目前为止，通过金属钯(Angew.Chem.Int.Ed.,2015,54,1270)，金属铜(Org.Lett.,2017,19,4187)催化完成了邻位二氟代烯烃的合成，反应方程式如下：
Figure BDA0002340446490000011
该路线虽然实现了邻位二氟烯烃的合成，但其方法并不能适用远程氟代芳基烯烃的制备，因此开发出新的研究方法合成远程氟代烯烃仍然是非常必要的。
发明内容
有鉴于此，本发明公开了一种合成三乙基(E)-1,1-二氟-7-苯基庚-6-烯-1,5,5-三羧酸的方法。以2-烯丙基-2-苯乙基丙二酸二乙酯及其衍生物为原料，在磷配体、无机碱以及有机溶剂存在下反应，得到本发明所述氟代烯烃类化合物三乙基(E)-1,1-二氟-7-苯基庚-6-烯-1,5,5-三羧酸。本发明方法采用钯催化一步即可完成，将烯烃异构化的同时，实现二氟烷基化，为该类化合物合成提供了直接有效的途径。
本发明所述一种远程氟代芳基烯烃1的制备方法，包括如下步骤：以化合物2和3为原料，在钯络合物、配体和碱存在下，有机溶剂中加热反应得到得到本发明所述氟代远程烯烃1。
反应方程式表示如下：
Figure BDA0002340446490000021
其中：R1、R2、R3各自独立选自氢、烷基、烷氧甲基、烷氧基、烷氧羰基、芳氧羰基、卤素、酰胺取代的任意一种。
进一步地，在上述技术方案中，更优选地R1选自氢、烷基、烷氧基或卤素；R2选自烷氧羰基、环状碳酸酯或烷基醇；R3选自烷氧羰基或烷基酰胺。
进一步地，在上述技术方案中，所述有机溶剂选自芳烃类溶剂、醚类溶剂、腈类溶剂、酮类溶剂、烷烃类溶剂、氯代烷烃溶剂、酰胺类溶剂、亚砜类溶剂中的任意一种或者多种的混合。更优选地采用四氢呋喃、二氯甲烷、二氯乙烷、二氧六环、乙腈、氯苯或甲苯。
进一步地，在上述技术方案中，所述钯络合物选自Pd(CH3CN)2Cl2、Pd(PPh3)2Cl2、Pd2(bda)3、[Pd(allyl)Cl]2或Pd(TFA)2。
进一步地，在上述技术方案中，所述配体选自Xantphos或DPEPhos。
进一步地，在上述技术方案中，所述碱选自乙酸钾、碳酸钾、碳酸钠、碳酸铯、磷酸二氢钠、磷酸二氢钾、磷酸氢二钠或磷酸氢二钾。优选自碳酸钾。
进一步地，在上述技术方案中，所述化合物2、化合物3与无机碱摩尔比为1：1-3：2-4；所述化合物2、钯络合物与配体摩尔比为1：0.03-0.06：0.06-0.12。
进一步地，在上述技术方案中，所述加热反应温度为60-100℃。
本发明方法采用钯催化一步即可完成，将烯烃异构化的同时，实现二氟烷基化，为该类化合物合成提供了直接有效的途径。为了进一步研究反应机理，做了如下对比实验：其中标准条件为实施例1-2条件。
Figure BDA0002340446490000022
根据以上对比实验，对比反应机理做了推测如下：
Figure BDA0002340446490000031
具体实施方式
下面结合具体实施案例对本发明作进一步详细说明。本实施案例在本发明技术方案的前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施案例。
为了更好地理解本发明而不是限制本发明的范围，在本申请中所用的表示用量、百分比的所有数字、以及其他数值，在所有情况下都应理解为以词语“大约”所修饰。因此，除非特别说明，否则在说明书和所附权利要求书中所列出的数字参数都是近似值，其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。
条件优化过程：
Figure BDA0002340446490000032
Figure BDA0002340446490000033
Figure BDA0002340446490000041
[a]Reaction condition:1a(0.1mmol),2a(0.2mmol),[Pd](5mol％),ligand(10mol％),Base(0.2mmol),solvent(1.0mL),under N2,80℃,24h.[b]Yield determinedby 19F NMP using PhCF3as an internal standard.[c]NR＝no reaction[d]under at 25℃.[e]under blue LED.
实施例1
Figure BDA0002340446490000042
在反应瓶内，向反应瓶中持续鼓入氮气，随后加入2-烯丙基-2-苯乙基丙二酸二乙酯2a(30.4mg,0.1mmol)、溴代二氟乙酸乙酯3a(40.2mg)、二(三苯基膦)二氯化钯(3.5mg)、4,5-双二苯基膦-9,9-二甲基氧杂蒽(5.78)、碳酸钾(27.6mg)及1.0mL乙腈，搅拌混合均匀后在80度条件反应12h后，直接柱层析分离得到目标产物1a，收率为72％。1H NMR(600MHz,CDCl3)δ7.41(d,J＝7.4Hz,2H),7.32(t,J＝7.4Hz,2H),7.26(t,J＝7.5Hz,1H),6.74(d,J＝16.6Hz,1H),6.49(d,J＝16.6Hz,1H),4.29-4.21(m,6H),2.20(t,J＝8.5Hz,2H),2.13-2.04(m,2H),1.49-1.43(m,2H),1.30-1.25(m,9H)；19F NMR(564MHz,CDCl3)δ-105.86(t,J＝16.9Hz,2F)；13C NMR(150MHz,CDCl3)δ170.18,164.08(t,J＝32.9Hz),136.30,131.56,128.55,127.99,126.52,125.73,115.87(t,J＝249.1Hz),62.79,61.70,59.21,34.95,34.49(t,J＝23.1Hz),16.64,13.98,13.85；HRMS(ESI)m/z calcd for C22H29F2O6[M+H+]427.1927,found 427.1920.
综合上述核磁、质谱测试结果，可以确定目标化合物1a为三乙基(E)-1,1-二氟-7-苯基庚-6-烯-1,5,5-三羧酸。
实施例2
Figure BDA0002340446490000051
在反应瓶内，向反应瓶中持续鼓入氮气，随后加入2-烯丙基-2-(4-甲氧基)苯乙基丙二酸二乙酯2b(32.0mg,0.1mmol)、溴代二氟乙酸乙酯3a(40.2mg)、二(三苯基膦)二氯化钯(3.5mg)、4,5-双二苯基膦-9,9-二甲基氧杂蒽(5.78)、碳酸钾(27.6mg)及1.0mL乙腈，搅拌混合均匀后在80度条件反应12h后，直接柱层析分离得到目标产物1b，收率为78％。1HNMR(600MHz,CDCl3)δ7.35(d,J＝8.8Hz,2H),6.86(d,J＝8.6Hz,2H),6.58(d,J＝16.6Hz,1H),6.42(d,J＝16.6Hz,1H),4.29(q,J＝7.3Hz,2H),4.24–4.20(m,4H),3.81(s,3H),2.18(t,J＝8.5Hz,2H),2.12-2.04(m,2H),1.47-1.42(m,2H),1.29(t,J＝7.0Hz,3H),1.25(t,J＝7.0Hz,6H)；19F NMR(564MHz,CDCl3)δ-105.87(t,J＝15.9Hz,2F)；13C NMR(150MHz,CDCl3)δ170.34,164.10(t,J＝32.9Hz),159.48,130.96,129.11,127.75,123.36,115.90(t,J＝248.9Hz),113.94,62.79,61.65,59.15,55.29,34.95,34.51(t,J＝23.0Hz),16.63,14.00,13.87；HRMS(ESI)m/z calcd for C23H31F2O7[M+H+]457.2032,found 457.2030.
实施例3
采用实施例1-2相同的反应条件，仅仅对反应底物2进行改变，得到系列产品1c-1o，具体结果如下：(其中，Rf＝CF2CO2Et)
Figure BDA0002340446490000061
实施例4
采用实施例1-2相同的反应条件，仅仅对反应底物3进行改变，得到系列产品1p-1w，具体结果如下：
Figure BDA0002340446490000062
典型化合物表征如下：
Figure BDA0002340446490000071
diethyl(E)-2-(4,4-difluoro-5-oxo-5-(phenylamino)pentyl)-2-styrylmalonate(1p):
Colorless oil,42.3mg,(45％yield).1H NMR(600MHz,CDCl3)δ7.92(br,1H),7.53(d,J＝7.7Hz,2H),7.40(d,J＝7.5Hz,2H),7.36-7.30(m,4H),7.27-7.26(m,1H),7.18(t,J＝7.6Hz,1H),6.73(d,J＝16.6Hz,1H),6.49(d,J＝16.6Hz,1H),4.24-4.20(m,4H),2.25-2.18(m,4H),1.54-1.49(m,2H),1.25(t,J＝7.0Hz,6H)；19F NMR(564MHz,CDCl3)δ-105.43(d,J＝17.3Hz,2F)；13C NMR(150MHz,CDCl3)δ170.24,161.84(t,J＝28.1Hz),136.32,135.84,131.63,129.18,128.58,127.99,126.58,125.76,125.56,120.18,118.00(t,J＝252.3Hz),61.74,59.26,34.96,33.73(t,J＝23.0Hz),16.76,14.01；HRMS(ESI)m/z calcdfor C26H30F2NO5[M+H+]474.2087,found 474.2073.
Figure BDA0002340446490000072
diethyl(E)-2-(5-(dipropylamino)-4,4-difluoro-5-oxopentyl)-2-styrylmalonate(1q):
Colorless oil,52.9mg,(55％yield).1H NMR(600MHz,CDCl3)δ7.42(d,J＝7.6Hz,2H),7.32(t,J＝7.5Hz,2H),7.25(t,J＝7.4Hz,1H),6.75(d,J＝16.6Hz,1H),6.50(d,J＝16.6Hz,1H),4.26-4.20(m,4H),3.34(t,J＝7.9Hz,2H),3.24(t,J＝7.6Hz,2H),2.22(t,J＝8.5Hz,2H),2.17-2.13(m,2H),1.60-1.52(m,4H),1.51-1.47(m,2H),1.26(t,J＝7.3Hz,6H),0.88-0.85(m,6H)；19F NMR(564MHz,CDCl3)δ-99.92(t,J＝18.3Hz,2F)；13C NMR(150MHz,CDCl3)δ170.33,162.95(t,J＝28.8Hz),136.46,131.45,128.50,127.86,126.55,125.91,119.34(t,J＝253.1Hz),61.60,59.35,49.08,48.47,35.12,34.86(t,J＝23.5Hz),22.11,20.18,16.66,13.98,11.22,10.93；HRMS(ESI)m/z calcd for C26H38F2NO5[M+H+]482.2713,found 482.2709.
Figure BDA0002340446490000073
diethyl(E)-2-(4,4-difluoro-5-oxo-5-(pyrrolidin-1-yl)pentyl)-2-styrylmalonate(1r):
Colorless oil,55.9mg,(62％yield).1H NMR(600MHz,CDCl3)δ7.42(d,J＝5.3Hz,2H),7.32(t,J＝7.5Hz,2H),7.26-7.24(m,1H),6.74(d,J＝16.6Hz,1H),6.50(d,J＝16.6Hz,1H),4.26-4.20(m,4H),3.64(t,J＝6.7Hz,2H),3.47(t,J＝7.0Hz,2H),2.22(t,J＝8.5Hz,2H),2.16-2.12(m,2H),1.94-1.90(m,2H),1.84-1.81(m,2H),1.52-1.46(m,2H),1.26(t,J＝7.0Hz,6H)；19F NMR(564MHz,CDCl3)δ-103.43(t,J＝18.7Hz,2F)；13C NMR(150MHz,CDCl3)δ170.32,162.04(t,J＝29.8Hz),136.44,131.47,128.51,127.88,126.55,125.91,118.77(t,J＝251.6Hz),61.62,59.35,47.28,46.51,35.10,34.24(t,J＝23.0Hz),26.44,23.22,16.61,13.99；HRMS(ESI)m/z calcd for C24H32F2NO5[M+H+]452.2243,found452.2244.
Figure BDA0002340446490000081
diethyl(E)-2-(4,4-difluoro-5-morpholino-5-oxopentyl)-2-styrylmalonate(1s):
Colorless oil,55.1 mg,(59％yield).1H NMR(600MHz,CDCl3)δ7.42(d,J＝7.6Hz,2H),7.32(t,J＝7.5Hz,2H),7.27-7.24(m,1H),6.75(d,J＝16.6Hz,1H),6.50(d,J＝16.6Hz,1H),4.25-4.20(m,4H),3.70-3.66(m,6H),3.61(t,J＝4.9Hz,2H),2.22(t,J＝8.5Hz,2H),2.17-2.12(m,2H),1.54-1.48(m,2H),1.26(t,J＝7.0Hz,6H)；19F NMR(564MHz,CDCl3)δ-99.53(t,J＝9.7Hz,2F)；13C NMR(150MHz,CDCl3)δ170.31,161.80(t,J＝29.5Hz),136.44,131.51,128.54,127.92,126.56,125.90,119.22(t,J＝252.7Hz),66.75,66.68,61.65,59.35,46.44,43.25,35.13,34.61(t,J＝22.9Hz),16.62,14.01；HRMS(ESI)m/zcalcd for C24H32F2NO6[M+H+]468.2192,found 468.2191.
Figure BDA0002340446490000082
diethyl(E)-2-(5-(4-(tert-butoxycarbonyl)piperazin-1-yl)-4,4-difluoro-5-oxopentyl)-2-styrylmalonate(1u):
Colorless oil,63.3 mg,(56％yield).1H NMR(600MHz,CDCl3)δ7.42(d,J＝7.4Hz,2H),7.32(d,J＝7.4Hz,2H),7.26-7.24(m,1H),6.74(d,J＝16.6Hz,1H),6.50(d,J＝16.6Hz,1H),4.26-4.20(m,4H),3.64(s,2H),3.56(s,2H),3.43(s,4H),2.22(d,J＝5.1Hz,2H),2.17-2.13(m,2H),1.51-1.48(m,2H),1.46(s,9H),1.26(t,J＝7.0Hz,6H)；19F NMR(564MHz,CDCl3)δ-99.39(t,J＝17.3Hz,2F)；13C NMR(150MHz,CDCl3)δ170.30,161.89(t,J＝28.5Hz),154.40,136.42,131.50,128.53,127.91,126.54,125.88,119.20(t,J＝253.1Hz),80.37,61.64,59.33,45.60,42.87,35.11,34.60(t,J＝22.8Hz),28.31,16.61,14.00；HRMS(ESI)m/z calcd for C29H41F2N2O7[M+H+]567.2876,found 567.2877.
Figure BDA0002340446490000091
triethyl(E)-1-fluoro-7-phenylhept-6-ene-1,5,5-tricarboxylate(1v):
Colorless oil,35.1mg,(43％yield).1H NMR(600MHz,CDCl3)δ7.41(d,J＝7.4Hz,2H),7.33(d,J＝7.5Hz,2H),7.27-7.25(m,1H),6.75(d,J＝16.6Hz,1H),6.49(d,J＝16.6Hz,1H),4.92-4.81(m,1H),3.24-4.21(m,6H),2.22-2.16(m,2H),1.94-1.87(m,2H),1.47-1.42(m,2H),1.26(t,J＝7.1Hz,9H)；19F NMR(564MHz,CDCl3)δ-199.13--192.31(m,1F)；13C NMR(150MHz,CDCl3)δ170.33(d,J＝2.1Hz),169.83(d,J＝23.5Hz),136.37,131.44,128.56,127.96,126.54,125.94,89.07(t,J＝183.3Hz),61.67,61.48,59.25,34.97,32.58(t,J＝21.2Hz),19.47,14.10,14.02；HRMS(ESI)m/z calcd for C22H30FO6[M+H+]409.2021,found 409.2007.
Figure BDA0002340446490000092
5,5-diethyl 1-methyl(E)-1,1-difluoro-7-phenylhept-6-ene-1,5,5-tricarboxylate(1w):
Colorless oil,62.6mg,(76％yield).1H NMR(600MHz,CDCl3)δ7.42(d,J＝7.3Hz,2H),7.33(d,J＝7.5Hz,2H),7.28-7.25(m,1H),6.73(d,J＝16.7Hz,1H),6.49(d,J＝16.7Hz,1H),4.25(q,J＝7.0Hz,4H),3.82(s,3H),2.20(t,J＝8.3Hz,2H),2.13-2.05(s,2H),1.48-1.45(m,2H),1.26(t,J＝7.3Hz,6H)；19F NMR(564MHz,CDCl3)δ-105.60(t,J＝17.3Hz,2F)；13C NMR(150MHz,CDCl3)δ170.18,164.57(t,J＝32.8Hz),136.30,131.58,128.57,128.00,126.54,125.71,115.92(t,J＝249.2Hz),61.72,59.21,53.28,34.90,34.49(t,J＝23.1Hz),16.60,13.99；HRMS(ESI)m/z calcd for C21H27F2O6[M+H+]413.1770,found 413.1766.
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (3)

1.一种远程氟代芳基烯烃1的制备方法，其特征在于，包括如下步骤：以化合物2和3为原料，在钯络合物、配体和碱存在下，有机溶剂中加热反应得到远程氟代芳基烯烃1；反应方程式表示如下：
Figure FDA0003416538420000011
其中：R1选自氢、烷基、烷氧基或卤素；R2选自烷氧羰基；R3选自烷氧羰基；
所述有机溶剂选自四氢呋喃、二氯甲烷、二氯乙烷、二氧六环、乙腈、氯苯或甲苯；钯络合物选自Pd(PPh3)2Cl2、Pd(CH3CN)2Cl2、Pd2(bda)3、[Pd(allyl)Cl]2或Pd(TFA)2；配体选自Xantphos或DPEPhos；碱选自乙酸钾、碳酸钾、碳酸钠、碳酸铯、磷酸二氢钠、磷酸二氢钾、磷酸氢二钠或磷酸氢二钾；所述加热反应温度为60-100℃。
2.根据权利要求1所述远程氟代芳基烯烃1的制备方法，其特征在于：所述碱选自碳酸钾。
3.根据权利要求1所述远程氟代芳基烯烃1的制备方法，其特征在于：所述化合物2、化合物3与无机碱摩尔比为1：1-3：2-4；所述化合物2、钯络合物与配体摩尔比为1：0.03-0.06：0.06-0.12。
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