CN110872264B - 含环外z,e-双烯顺式四氢苯并呋喃类化合物及其合成方法 - Google Patents
含环外z,e-双烯顺式四氢苯并呋喃类化合物及其合成方法 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机合成领域,具体涉及一种含环外(Z,E)-双烯单元的顺式四氢苯并呋喃结构化合物、其制备方法及应用。
背景技术
顺式四氢苯并呋喃结构化合物是一类非常重要的、广泛存在于天然产物以及有活性化合物的一类结构如Sorbicillactone A(Angew. Chem.,Int.Ed.2008,47,1935-1937)、(+)-Paeonilactone B(Tetrahedron 2005,61,7252-7265)。其中含有环外双键结构的骨架结构III还被证明是NF-κB信号传导通路的抑制剂(ACS Med.Chem.Lett.2012,3, 459-464)。
目前,含环外双烯单元的顺式四氢苯并呋喃结构化合物的方法仍然没有被报道。因此,发展该类化合物的高效合成,可以得到一类具有特有结构的骨架结构,对于药物先导化合物的筛选具有重要的作用。
发明内容
本发明的目的在于提供了一种含环外(Z,E)-双烯单元的顺式四氢苯并呋喃结构化合物、其制备方法及应用。本发明中,所述化合物结构新颖,具体结构为在铑催化剂存在下,一步即可完成对上述化合物的合成,高选择性得到含环外(Z,E)-双烯单元的顺式四氢苯并呋喃结构化合物,合成方法目前尚未有报道。该方法具有如下优势:本发明可以通用,反应条件温和,成本低,高立体选择性和高区域活性,反应路径合理,高效制备该类型的化合物。
一种含环外(Z,E)-双烯顺式四氢苯并呋喃类化合物,具体结构如下:
其中,R选自烷基、芳基或卤素,R1,R2各自独立地选自芳基或烷基、或R1和R2共同构成芳环。
本发明还提供了上述结构化合物的合成方法,合成路线如下:
包括如下步骤:
将化合物1、化合物2和铑催化剂混合,在有机溶剂中,加热反应得到化合物3。
进一步地,所述铑催化剂为Cp*Rh(OAc)2.H2O或[Cp*RhCl2]2/ NaOAc原位产生的铑催化剂。
进一步地,在上述技术方案中,所述化合物1、化合物2、铑催化剂的摩尔比为2.0-3.0∶1.0∶0.04-0.10。
进一步地,在上述技术方案中,有机溶剂选自含氯溶剂,例如二氯甲烷、氯仿、1,2-二氯乙烷或氯苯等,优选溶剂为1,2-二氯乙烷。
进一步地,在上述技术方案中,所述加热反应温度为60-90℃。
进一步地,在上述技术方案中,反应无需惰性气体保护,可在空气中直接进行。
为了对反应机理进行研究,做了如下对比试验,结果如下:
根据以上对比试验结果,推测的可能反应机理如下:
进一步地,在上述技术方案中,得到的产物进一步衍生如下(以 3aa和3ab为例):
本发明的第三个目的:在得到上述化合物3的基础上,将含环外 (Z,E)-双烯单元的顺式四氢苯并呋喃结构化合物用于NF-κB信号传导通路的抑制剂上,最好得到了IC50=26μM。
发明有益效果
本发明可以高选择性合成含环外(Z,E)-双烯单元的顺式四氢苯并呋喃结构化合物,本发明的优势在于:首次合成此类化合物,反应条件温和,效率高,反应路径合理,后处理简单。作为一类新的结构,在NF-κB信号传导通路的抑制上显示出了良好的活性。
附图说明
图1为实施例2得到化合物3ab对A549细胞的抑制率图;
图2为实施例8得到化合物3bb对A549细胞的抑制率图;
图3为实施例10得到化合物3mb对A549细胞的抑制率图。
图4为实施例12得到的化合物3eb的单晶图。
具体实施方式
以下结合具体实施例对本发明的技术方案作进一步详细说明,但本发明的保护范围并不局限于此。
反应条件的优化试验:(以1a和2a在铑催化下生成3a为例) 典型操作为,将化合物1a(0.2mmol)、铑催化剂(4.0mol%)、化合物 2a(0.2mmol,1.0eq),60-80℃反应直至通过薄层板(TLC)监测原料2a完全消失(9-12h);旋干溶剂,柱层析分离(洗脱剂:石油醚/ 乙酸乙酯体积比2:1),得到黄色固体3aa。反应优化结果如下:
需要说明的是:在反应标号1中,除了得到产物3aa外,自身偶联副产物3aa’分离达到26%。
通过以上反应条件优化,最终确定最佳反应条件为:在1,2-二氯乙烷溶剂中,采用Cp*Rh(OAc)2.H2O或[Cp*RhCl2]2在醋酸钠存在下反应。
实施例1:
化合物3aa的合成路线如下:
化合物3aa的合成步骤如下:
将化合物1a(0.6mmol,3.0eq)、Cp*Rh(OAc)2-H2O(0.02mmol, 0.1eq)、化合物2a(0.2mmol,1.0eq),60℃反应直至通过薄层板(TLC) 监测原料2a完全消失(约9h);旋干溶剂,柱层析分离(洗脱剂:石油醚/乙酸乙酯体积比2:1),得到55mg黄色固体3aa,熔点61-63℃,产率:85%。
1H NMR(600MHz,CDCl3):7.32(t,J=7.5Hz,2H),7.24-7.20(m, 3H),7.09(dd,J=11.9,1.7Hz,1H),6.59(d,J=10.2Hz,1H),6.52(d,J =11.9Hz,1H),6.03(d,J=10.2Hz,1H),4.52-4.43(m,2H),3.68(s,2H), 3.14-3.12(m,1H),2.59(dd,J=16.4,7.3Hz,1H),2.50(dd,J=16.4,6.1 Hz,1H),1.43(s,3H).13C NMR(100MHz,CDCl3):197.1,171.8,150.8,149.5,138.9,137.4,129.1,128.8,126.7,118.8,79.6,70.9,46.0,40.2, 39.4,24.4.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C20H20 NaO4 + 347.1254,Found:347.1248.
实施例2:
1H NMR(600MHz,CDCl3):7.32(t,J=7.5Hz,2H),7.24-7.20(m, 3H),7.07(dd,J=11.9,1.6Hz,1H),6.54(d,J=11.9Hz,1H),6.37(d,J =0.9Hz,1H),4.51(d,J=15.0Hz,1H),4.46(d,J=15.1Hz,1H),3.68 (s,2H),3.12-3.10(m,1H),1.79(s,3H),1.39(s,3H).13CNMR(150MHz, CDCl3):197.6,172.2,151.5,144.6,139.0,137.8,136.6,129.4,129.0,128.7,126.7,118.6,80.1,70.7,46.2,40.2,39.6,24.8,15.8.HRMS(ESI- TOF)m/z:[M+Na]+Calcd for Chemical Formula:C21H22NaO4 +361.1410, Found:361.1414.
实施例3:
1H NMR(600MHz,CDCl3):7.33(t,J=7.6Hz,2H),7.25-7.19(m, 3H),7.09(dd,J=11.9,1.8Hz,1H),7.03(s,1H),6.46(d,J=11.9Hz, 1H),4.58-4.41(m,2H),3.74-3.63(m,2H),3.15-3.13(m,J=6.0Hz,1H), 2.77(dd,J=16.3,7.1Hz,1H),2.63(dd,J=16.3,5.8Hz,1H),1.46(s, 3H).13C NMR(150MHz,CDCl3):188.9,172.1,150.0,149.3,138.7,137.0,130.3,129.2,128.8,126.8,125.0,119.3,82.2,71.1,46.1,40.1, 39.3,24.2.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C20H19NaO4 +425. 0359,Found:425.0354.
实施例4:
1H NMR(400MHz,CDCl3):7.35-7.27(m,5H),7.25-7.15(m,5H), 7.07(d,J=11.8Hz,1H),6.58(d,J=10.3Hz,1H),6.48(d,J=11.9Hz, 1H),6.05(d,J=10.3Hz,1H),4.55-4.44(m,2H),3.75-3.63(m,2H), 3.24(m,1H),3.08(d,J=13.7Hz,1H),2.96(d,J=13.7Hz,1H),2.51 (dd,J=16.5,6.5Hz,1H),2.23(dd,J=16.5,6.2Hz,1H).13C NMR(150MHz,CDCl3):197.1,172.2,150.5,148.4,138.9,137.4,135.3,130.6, 130.3,129.7,129.1,128.7,128.6,127.3,126.6,118.7,82.2,70.9,44.1, 43.9,40.1,39.4.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C26H24NaO4 + 423.1567,Found:423.1569.
实施例5:
1H NMR(600MHz,CDCl3):7.44-7.38(m,4H),7.35-7.33(m,1H), 7.30(t,J=7.6Hz,2H),7.21(t,J=7.4Hz,1H),7.17(d,J=7.5Hz,2H), 7.05(dd,J=11.9,1.7Hz,1H),6.61(d,J=10.2Hz,1H),6.47(d,J= 11.9Hz,1H),6.19(d,J=10.2Hz,1H),4.68-4.59(m,2H),3.68-3.62(m, 2H),3.51-3.49(m,1H),2.66(dd,J=16.4,6.9Hz,1H),2.61(dd,J= 16.4,6.1Hz,1H).13C NMR(150MHz,CDCl3):197.1,172.1,149.9, 148.0,141.2,138.8,137.2,130.1,129.8,129.0,128.7,128.5,126.7, 125.4,118.5,83.7,71.5,47.7,40.2,39.3.HRMS(ESI-TOF)m/z:[M+ Na]+Calcd for C25H22NaO4 +449.1410,Found:409.1406.
实施例6:
1H NMR(400MHz,CDCl3):7.32(t,J=7.3Hz,2H),7.24-7.20(m, 3H),7.07(d,J=11.8Hz,1H),6.57(d,J=11.9Hz,1H),4.45(d,J= 14.9Hz,1H),4.38(d,J=15.0Hz,1H),3.68(s,2H),3.15-3.13(m,1H), 2.75-2.47(m,6H),1.99-1.84(m,2H),1.43(s,3H).13C NMR(150MHz, CDCl3):194.8,172.2,162.5,151.2,139.6,139.0,137.6,129.4,129.1, 128.7,126.6,118.7,80.7,70.9,48.0,40.4,40.2,32.9,29.8,22.9,21.8. HRMS(ESI-TOF)m/z:[M+Na]+Chemical Formula:C23H24NaO4 +387. 1567,Found:387.1561.
实施例7:
1H NMR(600MHz,CDCl3):7.32(t,J=7.5Hz,2H),7.23-7.20(m, 3H),7.04(d,J=11.5Hz,1H),6.59(d,J=11.9Hz,1H),5.88(s,1H), 4.42(d,J=14.6Hz,1H),4.32(d,J=14.4Hz,1H),3.68(s,2H),3.38(m, 1H),2.68(td,J=13.0,4.5Hz,1H),2.59(dd,J=16.2,5.6Hz,1H),2.52 -2.43(m,2H),2.27(d,J=12.8Hz,1H),2.14-1.99(m,3H),1.98-1.91(m,1H),1.87-1.58(m,J=13.1Hz,1H),1.70-1.63(m,2H),1.61-1.54(m, 1H),1.39-1.23(m,3H),1.17-1.10(m,1H),0.93(s,3H).13C NMR(150 MHz,CDCl3):196.4,171.7,163.4,150.7,138.9,137.0,129.6,129.1, 128.7,126.7,125.2,118.2,84.4,71.2,50.8,50.5,47.9,41.3,40.3,39.7, 36.1,35.9,32.3,31.5,31.2,21.9,21.3,13.9.HRMS(ESI-TOF)m/z:[M +Na]+Calcd for C31H34NaO5 +509.2298,Found:509.2297.
实施例8:
1H NMR(600MHz,CDCl3):7.08-7.06(m,1H),6.62(d,J=11.9 Hz,1H),6.40(s,1H),4.56(d,J=14.9Hz,1H),4.47(d,J=15.0Hz,1H), 3.26-3.24(m,1H),2.71(dd,J=16.1,8.7Hz,1H),2.61(dd,J=16.1,6.1 Hz,1H),2.02(s,3H),1.80(s,3H),1.40(s,3H).13C NMR(150MHz, CDCl3)δ198.0,172.7,150.4,144.5,137.0,136.6,125.8,118.8,79.9, 70.7,46.0,39.8,25.0,21.0,15.8.HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C15H18NaO4 +285.1097,Found:285.1097.
实施例9:
1H NMR(600MHz,CDCl3):7.4-7.34(m,5H),7.00(d,J=12.0Hz, 1H),6.85(d,J=12.0Hz,1H),6.41(s,1H),4.60(d,J=15.2Hz,1H), 4.53(d,J=15.3Hz,1H),3.31-3.28(m,1H),2.75(dd,J=16.2,8.5Hz, 1H),2.63(dd,J=16.2,6.0Hz,1H),1.81(s,3H),1.42(s,3H).13C NMR (150MHz,CDCl3):197.7,172.1,152.6,144.5,138.1,136.6,136.1,131.7,128.5,128.4,128.3,118.7,80.0,70.8,46.4,39.7,24.9,15.8.HRMS(ESI -TOF)m/z:[M+H]+Calcd for C20H20NaO4 +325.1434,Found:325.1433.
实施例10:
1H NMR(600MHz,CDCl3):8.14(d,J=8.2Hz,1H),7.69-7.66(m, 1H),7.56-7.49(m,1H),7.41-7.39(m,1H),7.37-7.34(m,1H),6.82(d,J =12.0Hz,1H),6.42(m,1H),4.64(d,J=15.6Hz,1H),4.57(d,J=15.7 Hz,1H),3.29–3.22(m,1H),2.73(dd,J=16.1,9.1Hz,1H),2.58(dd,J =16.1,5.9Hz,1H),1.80(m,3H),1.40(s,3H).13C NMR(150MHz, CDCl3):197.7,169.6,154.8,147.9,144.4,138.5,136.6,134.8,134.1, 132.7,129.3,128.6,124.9,118.5,80.1,70.9,46.4,39.7,24.9,15.8. HRMS(ESI-TOF)m/z:[M+Na]+Calcd forC20H19NaO6 +392.1105,Found: 392.1103.
实施例11
根据实施例1反应条件,采用化合物1a与不同的化合物2a-2r,反应结果如下:
实施例12
根据实施例1反应条件,采用不同的化合物1a-1q与化合物2b,反应结果如下:
实施例13
反应采用克级规模试验,参考实施例1反应条件,仅仅反应规模扩大,结果如下:
实施例14
化合物3aa到4aa的衍生化操作步骤:
将化合物3aa(0.1mmol)、10%Pd/C(0.015mmol,15mol%)加入反应瓶,抽换氢气3次,加入2mL甲醇,氢气鼓泡条件下室温反应2.5 小时。反应结束后旋干溶剂,柱层析分离(石油醚/乙酸乙酯体积比 2:1)得到黄色油状液体4aa,24mg,产率72%。
1H NMR(600MHz,CDCl3):7.32-7.27(m,2H),7.24-7.20(m,1H), 7.19-7.14(m,2H),3.99-3.93(m,1H),3.46-3.28(m,1H),3.05-2.94(m, 1H),2.77-2.61(m,2H),2.53-2.43(m,1H),2.42-1.76(m,6H),1.70-1.40 (m,3H),1.33-1.26(m,3H).13C NMR(150MHz,CDCl3):213.4,213.3, 212.6,179.8,138.7,138.6,128.9,128.6,128.5,126.6,126.6,82.0,82.0, 80.9,80.7,71.0,70.9,70.4,70.3,49.3,49.3,47.4,47.3,47.3,47.2,47.2,47.0,45.2,45.0,42.3,42.2,41.4,41.1,38.2,38.0,37.8,37.6,35.7,34.9, 34.3,32.9,30.2,30.1,30.1,29.8,29.8,27.4,27.4,27.6,24.9,24.8. HRMS(ESI-TOF)m/z:[M+Na]+Calcd for C20H26NaO4 +353.1723,Found: 353.1722.
化合物3ab到5ab的操作步骤:
将3ab(0.2mmol)加入到MeOH(5mL)中,滴入1滴浓硫酸。反应在室温下进行40小时,加入20毫升水,用乙酸乙酯萃取,硫酸钠干燥,旋蒸后柱层析得到黄色油状液体5ab,70mg,收率99%。
1H NMR(600MHz,CDCl3):7.47(d,J=11.6Hz,1H),7.19(t,J= 7.4Hz,2H),7.14(t,J=7.3Hz,1H),7.06(d,J=7.3Hz,2H),6.95(s, 1H),6.47(s,1H),6.27(d,J=11.6Hz,1H),4.38(s,2H),3.77(s,3H), 3.53(s,2H),2.20(s,3H),2.05(s,3H).13C NMR(150MHz,CDCl3):155.8, 150.9,139.9,139.4,134.4,132.7,129.1,128.7,128.4,127.4,126.5, 126.3,122.6,110.6,67.0,55.6,40.2,18.6,16.0.HRMS(ESI-TOF)m/z: [M+Na]+ChemicalFormula:C22H24NaO4 +375.1567,Found:375.1556.
化合物3ab到6ab的操作步骤:
将化合物3ab(1mmol,1equiv)、K2CO3(3mmol,3equiv),MeI(6 mmol,6equiv)加入到N,N-二甲基甲酰胺(5mL)中室温反应10小时。加入水淬灭,用乙酸乙酯萃取,硫酸钠干燥,旋蒸后柱层析得到黄色油状液体6ab,350mg,收率99%。
1H NMR(600MHz,CDCl3):7.31(t,J=7.6Hz,2H),7.22(t,J= 7.4Hz,1H),7.19(d,J=7.3Hz,2H),6.97-7.00(m,1H),6.42(d,J=11.8 Hz,1H),6.37(d,J=1.2Hz,1H),4.51(d,J=14.8Hz,1H),4.45(d,J= 14.9Hz,1H),3.70(s,3H),3.68(s,2H),3.13-3.10(m,1H),2.60(dd,J= 16.2,8.1Hz,1H),2.49(dd,J=16.2,6.0Hz,1H),1.79(m,J=1.2Hz, 3H),1.39(s,3H).13C NMR(150MHz,CDCl3):197.6,167.6,150.2, 144.6,139.1,136.5,135.3,130.5,129.0,128.7,126.6,118.4,80.0,70.7, 51.7,46.1,40.6,39.6,24.8,15.8.HRMS(ESI-TOF)m/z:[M+Na]+ Chemical Formula:C22H24NaO4 +375.1567,Found:375.1560.
化合物6ab到7ab的操作步骤:
将化合物6ab(0.2mmol)、PCC(0.8mmol)加入到二氯甲烷(2 mL)中,70℃反应24小时。待反应结束后旋干溶剂,柱层析分离(石油醚/乙酸乙酯体积比2:1)得到黄色油状液体7ab,46mg,产率63%。
1H NMR(600MHz,CDCl3):7.91(dd,J=12.2,1.9Hz,1H),7.35(t, J=7.6Hz,2H),7.28-7.27(m,1H),7.20(d,J=7.2Hz,2H),6.48(d,J= 1.3Hz,1H),6.37(d,J=12.2Hz,1H),3.80(s,3H),3.79(s,2H),3.39- 3.34(m,1H),2.57(dd,J=16.0,6.3Hz,1H),2.48(dd,J=16.0,10.1Hz, 1H),1.85(d,J=1.2Hz,3H),1.53(s,3H).13C NMR(150MHz,CDCl3):196.1,169.1,166.7,141.5,140.5,137.4,137.3,133.8,133.0,130.5, 129.2,128.9,127.1,78.8,52.4,42.7,41.0,39.3,27.8,15.9.HRMS (ESI-TOF)m/z:[M+Na]+ChemicalFormula:C22H22NaO5 +389.1359, Found:389.1350.
实施例15
对化合物3ab,3bb,3mb进行了NF-κB信号传导通路的抑制探究。测试了几类化合物对肺癌A549细胞的体外抑制作用。实验结果如下所示,化合物3ab的IC50=26μM的;化合物3bb的IC50=45μM;化合物3mb的IC50=107μM。
基于以上三种化合物在NF-κB信号传导通路中体现出较好的抑制作用,可以作为相应的母体结构筛选具有更高活性的先导化合物,对于NF-κB信号传导通路抑制剂的开发具有重要的潜在价值。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,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)
2.根据权利要求1所述的合成方法,其特征在于:所述化合物1、化合物2、铑催化剂的摩尔比为2.0-3.0:1.0:0.04-0.10。
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