CN114524753B - 一种多取代异羟肟酸衍生物的合成方法 - Google Patents

一种多取代异羟肟酸衍生物的合成方法 Download PDF

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CN114524753B
CN114524753B CN202210170647.3A CN202210170647A CN114524753B CN 114524753 B CN114524753 B CN 114524753B CN 202210170647 A CN202210170647 A CN 202210170647A CN 114524753 B CN114524753 B CN 114524753B
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宣俊
李倩
蔡宝贵
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Abstract

本发明公开了一种多取代异羟肟酸衍生物的合成方法，在光照条件下，利用醛1、亚硝基化合物2与芳基重氮酯化合物3在氮杂环卡宾和DBU催化的条件下进行反应。实验结果表明，当反应分别使用DCM和THF做溶剂时，可以选择性的获得多取代异羟肟酸衍生物4和5。本方法使用可见光作为绿色能源进行驱动，反应条件温和，易于操作，并能通过流动光化学的方法进行大量合成。

Description

一种多取代异羟肟酸衍生物的合成方法
技术领域
本发明属于有机合成领域，具体涉及一种多取代异羟肟酸衍生物的合成方法。
背景技术
异羟肟酸是强金属离子螯合剂，具有广泛的生物活性，以及抗真菌、抗炎和抗哮喘等特性，同时异羟肟酸还被认为是基质金属蛋白酶的有效抑制剂。此外，在过去几年中科研工作者们也相继开发了许多异羟肟酸的应用，因此开发绿色、高效且简便的异羟肟酸的合成方法在现实生活中具有一定的意义。
由于异羟肟酸衍生物的广泛应用，有机化学家们也相继的开发了许多合成异羟肟酸衍生物的方法。异羟肟酸衍生物通常是使用硝基化合物或者羟胺衍生物等与羧酸在溶液中进行合成。然而，这些方法大多使用到了非常昂贵的羟胺试剂、过渡金属催化剂、或者需要过量添加剂等。
发明内容
本课题组通过研究发现，在结合氮杂环卡宾(NHC)催化和可见光光催化的条件下，醛、亚硝基化合物与芳基重氮酯化合物可以通过一锅多组分的方法进行反应，从而为多取代异羟肟酸衍生物的一步合成提供了温和的反应途径。同时我们也尝试了使用绿色LED灯作为光源，结果表明反应速率会急速下降。
基于以上研究背景，本发明提供了一种多取代异羟肟酸衍生物的合成方法，在氮杂环卡宾和光催化结合的条件下，利用醛、亚硝基化合物和芳基重氮酯分别在二氯甲烷和四氢呋喃中通过一锅多组分的方法进行反应，简便的制备了各种多取代异羟肟酸衍生物。本方法不需要对中间体进行分离，通过一锅多组分的方法即可实现。
本发明多取代异羟肟酸衍生物的合成方法，将醛1、亚硝基化合物2、芳基重氮酯化合物3、氮杂环卡宾和DBU于溶剂DCM或THF中，在光照条件下进行反应，分离提纯后得到目标产物4或5。
合成路线如下所示：
醛1中的取代基R1为甲基、乙基、丙基、丁基、异丙基、环己基、烯丙基、酯基、芳基、萘、吡啶或噻吩。
亚硝基化合物2中的取代基Ar1为芳基、吡啶或嘧啶。
芳基重氮酯化合物3中的取代基R2为酯基或芳基，取代基Ar2为芳基。
所述分离提纯是通过硅胶柱层析分离纯化的方式，洗脱液为石油醚和乙酸乙酯，体积比5:1-3:1。
相较于现有技术，本发明的有益效果体现在：
1、所使用的原料容易制备，并且醛和亚硝基苯可以商业购买。
2、通过一锅多组分即可实现，无需对中间体进行分离。
3、反应条件温和，易于操作，并能通过流动光化学的方法进行大量合成。
4、氮气作为唯一副产物，符合绿色化学理念。
具体实施方式
下面结合具体实施例对本发明技术方案作进一步的详细说明。
实施例1：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：68％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.50(d,J＝7.0Hz,2H),7.37–7.31(m,4H),7.30–7.19(m,9H),5.61(s,1H),3.62(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.4,169.1,140.5,134.1,133.5,130.7,129.5,128.9,128.8,128.6,128.5,127.9,127.9,126.6,83.9,52.2.
高分辨：计算值：[M+H]+＝362.1387，实测值：362.1391.
实施例2：
在10mL反应瓶中，将醛(0.1mmol,15.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：41％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.07(s,1H),7.78(d,J＝8.4Hz,2H),7.69(d,J＝8.5Hz,1H),7.56–7.45(m,3H),7.35–7.19(m,10H),5.65(s,1H),3.62(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.5,169.1,140.6,134.2,133.5,132.3,131.4,129.9,129.5,129.0,128.9,128.6,127.9,127.6,127.6,127.5,126.6,126.5,125.3,52.3.
高分辨：计算值：[M+H]+＝412.1543，实测值：412.1536.
实施例3：
在10mL反应瓶中，将醛(0.1mmol,9.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：51％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.49(s,1H),7.40–7.29(m,10H),7.04(d,J＝3.6Hz,1H),6.45–6.40(m,1H),5.53(s,1H),3.62(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.2,158.8,145.7,145.6,139.5,133.0,129.7,128.9,128.6,128.1,126.2,118.9,111.5,84.2,52.3.
高分辨：计算值:[M+H]+:352.1179,实测值：352.1174.
实施例4：
在10mL反应瓶中，将醛(0.1mmol,11.2mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：53％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.70(d,J＝3.7Hz,1H),7.50(d,J＝3.8Hz,1H),7.43–7.29(m,10H),7.02–6.98(m,1H),5.52(s,1H),3.61(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.1,162.4,139.7,135.2,134.3,132.9,132.3,129.7,128.9,128.7,128.6,128.2,126.9,126.5,84.2,52.3.
高分辨：计算值：[M+H]+＝368.0951，实测值：368.0945.
实施例5：
在10mL反应瓶中，将醛(0.1mmol,10.7mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：52％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.74(s,1H),8.60(d,J＝5.4Hz,1H),7.89–7.84(m,1H),7.43–7.32(m,5H),7.31–7.22(m,6H),5.46(s,1H),3.63(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝168.8,166.8,151.2,149.8,139.1,136.4,132.8,129.8,129.2,128.7,128.5,128.2,126.0,122.6,83.7,52.4.
高分辨：计算值：[M+H]+＝363.1339，实测值：363.1330.
实施例6：
在10mL反应瓶中，将醛(0.1mmol,13.4mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝4:1]，即得到纯净的产物，黄色油状，产率：49％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.41–7.32(m,7H),7.31–7.24(m,5H),7.21–7.16(m,3H),5.31(s,1H),3.64(s,3H),3.16–2.64(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.4,141.1,138.9,133.2,129.7,128.9,128.8,128.5,128.4,128.3,127.7,126.0,125.4,83.3,52.3,35.4,30.6.
高分辨：计算值：[M+H]+＝390.1700.，实测值：390.1699.
实施例7：
在10mL反应瓶中，将醛(0.1mmol,7.0mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝4:1]，即得到纯净的产物，黄色油状，产率：53％。
化合物12经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.47–7.41(m,2H),7.40–7.33(m,7H),7.31–7.26(m,1H),5.43(s,1H),3.67(s,3H),2.23(s,1H),1.15–1.07(m,1H),0.98–0.90(m,1H),0.89–0.81(m,1H),0.79–0.71(m,1H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝174.5,169.5,139.4,133.3,129.7,128.8,128.7,128.4,127.5,125.4,83.9,52.3,11.9,9.4,9.0.
高分辨：计算值：[M+H]+＝326.1387，实测值：326.1384。
实施例8：
在10mL反应瓶中，将醛(0.1mmol,11.2mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝4:1]，即得到纯净的产物，黄色油状，产率：48％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.44–7.35(m,7H),7.34–7.26(m,3H),5.37(s,1H),3.65(s,3H),2.82(s,1H),1.86–1.59(m,5H),1.57–1.45(m,1H),1.36(t,J＝10.7Hz,1H),1.29–1.06(m,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.4,133.5,129.6,128.9,128.8,128.3,127.8,125.7,83.6,52.3,41.3,28.8,28.7,25.7,25.5.
高分辨：计算值：[M+H]+＝368.1856，实测值：368.1855.
实施例9：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,18.5mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝4:1]，即得到纯净的产物，黄色油状，产率：71％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.52–7.48(m,2H),7.43–7.27(m,10H),7.21–7.17(m,2H),5.55(s,1H),3.64(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.3,169.1,139.7,133.8,133.2,132.0,131.0,129.7,128.9,128.7,128.6,128.0,127.6,121.4,84.1,52.4
高分辨：计算值：[M+H]+＝440.0492，实测值：440.0483.
实施例10：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,17.9mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：47％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.96(d,J＝6.7Hz,2H),7.53–7.48(m,2H),7.43–7.23(m,10H),5.51(s,1H),4.35(q,J＝7.1Hz,2H),3.60(s,3H),1.37(t,J＝7.1Hz,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.0,168.9,165.8,144.2,133.9,132.9,131.1,130.2,129.7,128.9,128.8,128.6,128.6,128.0,124.4,84.3,61.1,52.4,14.3.
高分辨：计算值：[M+H]+＝434.1598，实测值：434.1590.
实施例11：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.8mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：38％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.29(d,J＝6.9Hz,1H),7.71–7.66(m,1H),7.60(d,J＝8.1Hz,1H),7.54(d,J＝7.1Hz,2H),7.40–7.26(m,8H),7.13–7.07(m,1H),5.85(s,1H),3.68(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.8,169.7,154.1,148.2,138.0,134.5,133.4,131.0,129.5,128.8,128.6,128.5,127.9,122.2,119.8,85.0,52.3.
高分辨：计算值：[M+H]+＝363.1339，实测值：363.1331.
实施例12：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,30.9mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：61％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.50(d,J＝7.2Hz,2H),7.35(t,J＝7.4Hz,1H),7.30–7.20(m,9H),6.80(d,J＝8.7Hz,2H),5.54(s,1H),3.79(s,3H),3.62(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.6,169.0,160.6,140.5,134.3,130.7,130.2,128.9,128.9,127.8,127.8,126.5,125.5,114.0,55.3,52.2.
高分辨：计算值：[M+H]+＝392.1492，实测值：392.1489.
实施例13：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,38.1mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：62％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.48(d,J＝7.1Hz,2H),7.42(d,J＝8.5Hz,2H),7.32(d,J＝30.4Hz,6H),7.26–7.19(m,4H),5.57(s,1H),3.63(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.1,140.5,134.0,132.5,131.8,130.9,130.1,129.0,128.9,128.1,127.9,126.7,123.9,83.3,52.4.
高分辨：计算值：[M+H]+＝440.0492，实测值：440.0486.
实施例14：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,33.0mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：77％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.53–7.48(m,2H),7.37–7.21(m,8H),6.83–6.75(m,2H),6.71(d,J＝7.9Hz,1H),5.94(s,2H),5.48(s,1H),3.63(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.4,169.1,148.7,147.8,140.5,134.2,130.8,128.9,128.9,127.8,127.0,126.4,123.1,108.7,108.1,101.3,83.6,52.3.
高分辨：计算值：[M+H]+＝406.1285，实测值：406.1286.
实施例15：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,33.9mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：60％。
化合物20经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.82–7.73(m,4H),7.52–7.46(m,4H),7.42(d,J＝8.5Hz,1H),7.36–7.21(m,8H),5.77(s,1H),3.64(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.4,169.2,140.5,134.2,133.7,132.9,130.8,130.8,128.9,128.9,128.5,128.4,128.3,127.9,127.9,127.7,126.9,126.6,126.4,125.2,52.3.
高分辨：计算值：[M+H]+＝412.1543，实测值：412.1538.
实施例16：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,34.0mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：53％。
化合物21经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.54–7.47(m,2H),7.38–7.19(m,13H),5.52(s,1H),5.16–5.06(m,1H),1.85–1.37(m,8H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.2,168.8,140.6,134.3,133.6,130.7,129.3,128.9,128.9,128.5,127.8,127.8,126.5,84.2,78.4,32.5,32.2,23.5,23.5.
高分辨：计算值：[M+H]+＝416.1856，实测值：416.1844.
实施例17：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,32.6mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：62％。
化合物22经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.53–7.48(m,2H),7.36–7.20(m,13H),5.61(s,1H),4.26–4.16(m,1H),4.09–4.00(m,1H),2.43–2.35(m,2H),1.90(t,J＝2.7Hz,1H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝169.1,168.8,140.6,134.2,133.3,130.8,129.5,128.9,128.9,128.6,127.9,127.9,126.6,84.0,79.4,62.8,18.7.
高分辨：计算值：[M+H]+＝400.1543，实测值：400.1543.
实施例18：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升DCM中，随后加入芳基重氮酯(0.15mmol,40.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝5:1-3:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：42％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.12(d,J＝8.8Hz,2H),7.47(d,J＝8.6Hz,2H),7.38–7.30(m,3H),7.26–7.16(m,5H),7.15–7.05(m,4H),6.78(d,J＝8.7Hz,2H),6.12(s,1H),3.80(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝168.9,160.1,147.4,146.4,140.4,134.4,130.5,130.2,129.5,129.0,128.6,128.5,127.8,127.7,126.2,123.3,113.9,85.3,55.3.
高分辨：计算值：[M+H]+＝455.1601，实测值：455.1619.
实施例19：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝10:1]，即得到纯净的产物，黄色油状，产率：91％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.60(d,J＝6.8Hz,2H),7.47(d,J＝7.8Hz,2H),7.41–7.30(m,10H),7.22(t,J＝7.4Hz,1H),4.78(s,1H),3.91–3.82(m,2H),3.44–3.37(m,1H),3.34–3.27(m,1H),1.68–1.51(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.3,139.6,136.5,134.8,130.4,128.9,128.6,128.5,128.4,127.9,127.1,126.7,123.9,80.9,77.3,77.0,76.7,73.8,69.0,52.1,25.8,24.5.
高分辨：计算值：[M+H]+＝434.1962，实测值：434.1966.
实施例20：
在10mL反应瓶中，将醛(0.1mmol,15.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝10:1]，即得到纯净的产物，黄色油状，产率：71％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.19(s,1H),7.86–7.76(m,3H),7.66(d,J＝8.5Hz,1H),7.56–7.47(m,4H),7.38–7.30(m,7H),7.23(t,J＝7.4Hz,1H),4.72(s,1H),3.95–3.86(m,2H),3.67(s,3H),3.38–3.30(m,1H),3.28–3.19(m,1H),1.68–1.51(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.2,139.7,136.5,134.1,132.4,132.1,129.1,129.0,128.8,128.6,128.6,127.7,127.4,127.1,126.8,126.5,125.2,123.9,80.9,73.9,68.9,52.2,25.8,24.6.
高分辨：计算值：[M+H]+＝484.2118，实测值：484.2137.
实施例21：
在10mL反应瓶中，将醛(0.1mmol,10.7mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：47％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.90(s,1H),8.64(d,J＝3.3Hz,1H),7.97(d,J＝7.9Hz,1H),4.78(s,1H),3.89–3.80(m,2H),3.68(s,3H),3.45–3.38(m,1H),3.35–3.28(m,1H),1.67–1.51(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.2,166.0,151.2,149.3,138.8,136.4,136.1,130.8,129.1,128.7,128.6,127.2,127.1,123.7,122.9,81.0,74.2,68.9,52.2,25.8,24.6.高分辨：计算值：[M+H]+＝435.1914，实测值：435.1921.
实施例22：
在10mL反应瓶中，将醛(0.1mmol,15.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：61％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.00(d,J＝3.9Hz,1H),4.83(s,1H),4.01–3.92(m,2H),3.69(s,3H),3.57–3.50(m,1H),3.47–3.39(m,1H),1.93–1.83(m,2H),1.79–1.69(m,2H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,160.6,138.7,136.5,135.1,133.8,132.6,128.8,128.7,128.6,127.1,126.9,126.8,123.7,81.1,74.7,69.2,52.2,26.0,24.7.
高分辨：计算值：[M+H]+＝440.1526，实测值：440.1541.
实施例23：
在10mL反应瓶中，将醛(0.1mmol,11.2mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：74％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.47–7.31(m,9H),7.26–7.17(m,1H),4.84(s,1H),3.91–3.82(m,2H),3.70(s,3H),3.60–3.52(m,1H),3.50–3.41(m,1H),2.69(s,1H),1.89–1.46(m,12H),1.26(s,2H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,136.5,128.7,128.6,127.1,81.1,69.2,52.2,41.4,29.0,26.1,25.7,24.9.
高分辨：计算值：[M+H]+＝440.2431，实测值：440.2455.
实施例24：
在10mL反应瓶中，将醛(0.1mmol,10.2mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：68％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.55–7.24(m,10H),4.84(s,1H),4.37(q,J＝7.3Hz,2H),3.99(d,J＝5.8Hz,2H),3.69(s,3H),3.58–3.50(m,1H),3.48–3.38(m,1H),1.78–1.67(m,4H),1.37(d,J＝7.2Hz,2H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,162.3,159.9,136.4,136.3,129.1,128.7,128.6,127.1,121.5,81.1,69.1,62.2,52.2,25.9,24.5,14.0.
高分辨：计算值：[M+H]+＝430.1860，实测值：430.1884.
实施例25：
在10mL反应瓶中，将醛(0.1mmol,5.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：64％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.55–7.24(m,10H),4.84(s,1H),4.37(q,J＝7.3Hz,2H),3.99(d,J＝5.8Hz,2H),3.69(s,3H),3.58–3.50(m,1H),3.48–3.38(m,1H),1.78–1.67(m,4H),1.37(d,J＝7.2Hz,2H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,162.3,159.9,136.4,136.3,129.1,128.7,128.6,127.1,121.5,81.1,69.1,62.2,52.2,25.9,24.5,14.0.
高分辨：计算值：[M+H]+＝384.1805，实测值：384.1819.
实施例26：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,14.1mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：89％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.62(d,J＝7.0Hz,2H),7.49–7.31(m,12H),4.77(s,1H),3.87–3.77(m,2H),3.69(s,3H),3.43–3.36(m,1H),3.33–3.25(m,1H),1.64–1.50(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.4,138.2,136.5,134.5,131.9,130.7,129.0,128.7,128.6,128.4,128.0,127.1,127.1,124.5,81.0,74.2,69.0,52.2,25.8,24.6.
高分辨：计算值：[M+H]+＝468.1572，实测值：468.1573.
实施例27：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,14.1mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：86％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.69–7.59(m,3H),7.48–7.27(m,10H),7.20(d,J＝9.7Hz,1H),4.77(s,1H),3.85–3.76(m,2H),3.68(s,3H),3.42–3.34(m,1H),3.32–3.23(m,1H),1.63–1.49(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.6,140.7,136.5,134.6,134.4,130.8,129.8,128.7,128.6,128.4,128.0,127.1,126.4,122.7,120.8,81.0,74.4,68.9,52.2,25.8,24.5.
高分辨：计算值：[M+H]+＝468.1572，实测值：468.1572.
实施例28：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,18.5mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：84％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.63(d,J＝6.9Hz,2H),7.50–7.32(m,12H),4.77(s,1H),3.86–3.76(m,2H),3.69(s,3H),3.43–3.35(m,1H),3.33–3.24(m,1H),1.65–1.48(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.4,138.7,136.5,134.4,132.0,130.7,128.7,128.6,128.4,128.0,127.1,124.6,119.7,81.0,74.2,68.9,52.2,25.8,24.5.
高分辨：计算值：[M+H]+＝512.1067，实测值：512.1073.
实施例29：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,18.3mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：77％。
化合物26经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.65(d,J＝7.1Hz,2H),7.61–7.53(m,6H),7.46–7.29(m,11H),4.78(s,1H),3.94–3.83(m,2H),3.68(s,3H),3.45–3.37(m,1H),3.35–3.27(m,1H),1.67–1.55(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.4,140.1,139.5,138.7,136.5,134.8,130.5,128.8,128.6,128.6,128.4,127.9,127.5,127.5,127.1,127.0,123.8,81.0,74.0,69.0,52.2,25.9,24.6.
高分辨：计算值：[M+H]+＝510.2275，实测值：510.2269.
实施例30：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,21.1mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：70％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.87–7.68(m,8H),7.60(t,J＝7.4Hz,1H),7.52–7.31(m,10H),4.77(s,1H),3.89–3.78(m,2H),3.68(s,3H),3.43–3.34(m,1H),3.33–3.23(m,1H),1.68–1.47(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝195.6,171.3,168.8,143.1,137.6,136.5,134.6,134.5,132.4,131.1,130.9,129.9,128.7,128.6,128.4,128.3,128.0,127.1,120.9,81.0,74.7,68.9,52.2,25.8,24.6.
高分辨：计算值：[M+H]+＝538.2224，实测值：538.2224.
实施例31：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,17.9mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：88％。
化合物26经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝8.05(d,J＝8.8Hz,2H),7.69–7.64(m,4H),7.45(t,J＝7.3Hz,1H),7.40–7.32(m,7H),4.77(s,1H),4.38(q,J＝7.1Hz,2H),3.86–3.77(m,2H),3.69(s,3H),3.42–3.34(m,1H),3.32–3.23(m,1H),1.62–1.50(m,4H),1.40(t,J＝7.1Hz,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.3,168.6,165.9,143.4,136.5,134.5,130.9,130.4,128.7,128.6,128.4,128.0,127.6,127.1,121.2,81.0,74.6,68.9,61.0,52.2,25.8,24.5,14.3.
高分辨：计算值：[M+H]+＝506.2173，实测值：506.2173.
实施例32：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,31.5mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：82％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.63–7.57(m,2H),7.49–7.20(m,12H),5.26(s,1H),3.89–3.80(m,2H),3.70(s,3H),3.50–3.43(m,1H),3.35–3.27(m,1H),1.66–1.50(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.6,168.3,139.6,134.8,134.6,133.6,130.4,129.8,129.5,128.9,128.6,128.3,127.9,127.2,126.7,123.8,77.1,73.8,69.4,52.3,25.8,24.5.
高分辨：计算值：[M+H]+＝468.1572，实测值：468.1586.
实施例33：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,31.5mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：78％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.64–7.56(m,2H),7.46(d,J＝7.4Hz,2H),7.41–7.29(m,9H),7.25–7.20(m,1H),4.75(s,1H),3.87(t,J＝6.0Hz,2H),3.68(s,3H),3.46-3.38(m,1H),3.34–3.25(m,1H),1.69–1.52(m,4H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.9,168.2,139.6,135.0,134.8,134.5,130.5,128.9,128.7,128.4,128.4,127.9,126.8,123.9,80.2,73.8,69.2,52.3,25.8,24.5.
高分辨：计算值：[M+H]+＝468.1572，实测值：468.1589.
实施例34：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,36.9mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：81％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.60(d,J＝6.9Hz,2H),7.48(d,J＝7.9Hz,2H),7.42–7.30(m,10H),7.22(t,J＝7.4Hz,1H),4.76(s,1H),4.08(t,J＝6.7Hz,2H),3.92–3.80(m,2H),3.45–3.38(m,1H),3.34–3.26(m,1H),1.68–1.48(m,6H),1.26–1.16(m,6H),0.84(t,J＝6.7Hz,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.9,168.3,139.6,136.7,134.8,130.5,128.9,128.5,128.5,128.4,127.9,127.0,126.7,123.8,81.0,69.0,65.2,31.2,28.4,25.9,25.3,24.6,22.4,13.9.
高分辨：计算值：[M+H]+＝504.2744，实测值：504.2757.
实施例35：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,30.6mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：74％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.61(d,J＝6.9Hz,2H),7.48(d,J＝7.9Hz,2H),7.41–7.29(m,10H),7.22(t,J＝7.4Hz,1H),5.07–4.96(m,1H),4.72(s,1H),3.92–3.82(m,2H),3.46–3.38(m,1H),3.35–3.27(m,1H),1.67–1.54(m,4H),1.22(d,J＝6.3Hz,3H),1.10(d,J＝6.2Hz,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.4,168.3,139.6,136.7,134.8,130.4,128.9,128.4,128.4,127.9,127.0,126.7,123.8,81.1,73.9,68.9,68.6,25.9,24.6,21.7,21.4.
高分辨：计算值：[M+H]+＝462.2275，实测值：462.2289.
实施例36：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,32.1mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：77％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.60(d,J＝7.0Hz,2H),7.48(d,J＝7.9Hz,2H),7.41–7.31(m,10H),7.22(t,J＝7.4Hz,1H),5.02–4.93(m,1H),4.73(s,1H),3.90–3.81(m,2H),3.44–3.37(m,1H),3.34–3.25(m,1H),2.37–2.21(m,2H),2.09–1.86(m,2H),1.80–1.70(m,1H),1.65–1.54(m,5H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.2,168.3,139.6,136.6,134.8,130.5,128.9,128.5,128.4,127.9,127.1,126.8,123.8,80.9,69.5,69.0,30.2,30.0,25.9,24.6,13.4.
高分辨：计算值：[M+H]+＝474.2275，实测值：474.2292.
实施例37：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,32.4mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升THF中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝5:1]，即得到纯净的产物，黄色油状，产率：76％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.60(d,J＝8.5Hz,2H),7.48(d,J＝7.8Hz,2H),7.43–7.30(m,10H),7.22(t,J＝7.4Hz,1H),4.82(d,J＝12.1Hz,3H),4.55–4.46(m,2H),3.92–3.82(m,2H),3.48–3.40(m,1H),3.36–3.26(m,1H),1.60(d,J＝4.9Hz,7H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝170.5,168.3,139.6,139.4,136.6,134.8,130.5,128.9,128.6,128.5,128.4,127.9,127.1,126.8,123.8,113.0,81.0,73.9,69.0,68.0,25.9,24.6,19.2.
高分辨：计算值：[M+H]+＝474.2275，实测值：474.2291.
实施例38：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升Tetrahydropyran中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝10:1]，即得到纯净的产物，黄色油状，产率：51％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.61(d,J＝8.6Hz,2H),7.49(d,J＝7.9Hz,2H),7.43–7.31(m,10H),7.22(t,J＝7.4Hz,1H),4.82(s,1H),3.83(t,J＝6.4Hz,2H),3.70(s,3H),3.47–3.41(m,1H),3.37–3.29(m,1H),1.56–1.46(m,4H),1.32–1.25(m,2H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.4,168.3,139.6,136.6,134.8,130.5,128.9,128.6,128.6,128.4,127.9,127.1,126.7,123.8,81.0,74.1,69.5,52.2,29.1,27.6,22.3.
高分辨：计算值：[M+H]+＝448.2118，实测值：448.2134.
实施例39：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升2,5-Dihydrofuran中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝10:1]，即得到纯净的产物，黄色油状，产率：53％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.57(d,J＝7.1Hz,2H),7.44–7.28(m,12H),7.23(t,J＝7.3Hz,1H),5.87–5.77(m,1H),5.69–5.59(m,1H),4.78(s,1H),4.39(d,J＝7.0Hz,2H),3.96–3.85(m,2H),3.68(s,3H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝136.0,131.9,130.6,129.0,128.8,128.7,128.6,127.9,127.3,127.1,125.9,124.4,80.2,77.3,77.0,76.7,69.5,64.8,52.3.
高分辨：计算值：[M+H]+＝432.1805，实测值：432.1799.
实施例40：
在10mL反应瓶中，将醛(0.1mmol,10.6mg)、亚硝基化合物(0.1mmol,10.7mg)、NHC(0.005mmol,1.8mg)以及DBU(0.005mmol,0.76mg)加入1毫升1,4-Dioxane中，随后加入芳基重氮酯(0.15mmol,26.4mg)于蓝光照射下进行反应，TLC(用薄层层析色谱法)检测至反应完全后减压除去有机溶剂，用硅胶柱层析分离纯化[V(石油醚)：V(乙酸乙酯)＝20:1～5:1，本实施例优选V(石油醚)：V(乙酸乙酯)＝3:1]，即得到纯净的产物，黄色油状，产率：62％。
化合物经测试：
1H NMR(400MHz,CDCl3,300K):δ(ppm)＝7.63(d,J＝7.1Hz,2H),7.49(d,J＝9.0Hz,2H),7.44–7.30(m,10H),7.21(t,J＝7.4Hz,1H),4.95(s,1H),4.04(t,J＝4.6Hz,2H),3.69(s,3H),3.65–3.53(m,6H).
13C NMR(100MHz,CDCl3,300K):δ(ppm)＝171.2,168.3,139.8,136.4,134.6,130.6,128.9,128.7,128.6,128.6,127.9,127.3,126.9,124.1,81.3,73.7,70.5,69.0,68.5,52.2.
高分辨：计算值：[M+H]+＝450.1911，实测值：450.1920.

Claims (1)

1.一种多取代异羟肟酸衍生物的合成方法，其特征在于：
在氮杂环卡宾NHC和DBU的催化下，醛1和亚硝基化合物2首先通过Aldol类型反应生成N-羟基化合物；当使用DCM作溶剂时，芳基重氮酯化合物3在蓝光照射条件下产生的活性卡宾物种直接与N-OH化合物通过O-H插入产生目标化合物4；当使用THF作溶剂时，芳基重氮酯化合物3在蓝光照射条件下产生的活性卡宾物种首先被THF所捕获产生叶立德中间体，随后N-羟基化合物作为亲核试剂进攻叶立德中间体可产生目标多取代异羟肟酸衍生物5；
合成路线如下所示：
反应在蓝色LED灯的照射下通过一锅多组分反应进行；
醛1中的取代基R1为甲基、乙基、丙基、丁基、异丙基、环己基、烯丙基、酯基、芳基、吡啶或噻吩；
亚硝基化合物2中的取代基Ar1为芳基、吡啶或嘧啶；
芳基重氮酯化合物3中的取代基R2为酯基或芳基，取代基Ar2为芳基；
反应结束后分离提纯获得目标产物；所述分离提纯是通过硅胶柱层析分离纯化的方式，洗脱液为石油醚和乙酸乙酯，体积比5:1-3:1。
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