CN115403482A - 基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法 - Google Patents
基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种基于烯烃的自由基烷氧羰基化/羰基化反应获得β‑氨基/β‑氨基酮衍生物的方法。这种方法采用简单易合成的草酸肟酯和苯乙醛酸肟酯为双官能化试剂,建立了光催化合成β‑氨基酸酯和β‑氨基酮衍生物的方法,这些双功能试剂通过能量转移促进的N‑O键均裂和脱碳生成亚氨基和烷氧羰基/苯甲酰基自由基,利用普通芳烃、普通烯烃、α‑三氟甲基苯乙烯和β‑CF3‑1,3‑烯炔等不同种类的烯烃,以60%‑86%的产率获得高度功能化的β‑氨基酸酯和β‑氨基酮衍生物,为合成β‑氨基酸酯和β‑氨基酮衍生物提供了一种新的、高效的合成策略。
Description
技术领域
本发明涉及光催化反应,具体是一种基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法。
技术背景
β-氨基酸酯和β-氨基酮衍生物广泛存在于生物活性分子中,其中许多具有重要的生物活性,如抗癌、抗病毒、抗菌、抗真菌和抗精神病药物性质。这些结构单元在有机化学、制药和材料科学中占有重要地位,因为它们具有高度的生物学相关性,因此吸引了越来越多的兴趣。随着广泛的应用,开发高效的β-氨基酸酯和β-氨基酮衍生物的方法已成为合成化学家的一个有价值的课题。通常,氮杂迈克尔加成是由烯酸酯和烯基酮3制备β-氨基酸酯和β-氨基酮衍生物的替代方法;或者,β-(酰胺基)烯酸酯和β-(酰胺基)烯基酮的氢化是合成这些分子的另一种方法。然而,这些方法涉及一次操作一个官能团,并且需要预官能化的底物,这些基质的特殊性也限制了它们的进一步应用。
发明内容
本发明的目的是针对现有技术的不足,而提供一种基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法。这种方法简单、绿色,为合成β-氨基酸酯和β-氨基酮衍生物提供了一种新的、高效的合成策略。
实现本发明目的的技术方案是:
一种基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法,所述合成方法通式如下:
R2为-Me或-H或-OCH3或-F或-Cl或-Br或-I或-CN或-CF3或-NO2或-CH(CH3)2或-Ph或
R3为-OMe或-OEt或-Ph或-Me或-C(CH3)3;R4为-Ph或-Me或-C(CH3)3。
合成β-氨基酸酯/β-氨基酮衍生物过程为:
将0.2mmol普通芳烃、0.3mmol草酸肟酯、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解、并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得β-氨基酸酯和β-氨基酮衍生物。
所述普通芳烃为二苯基烯烃、单苯基烯烃、α-三氟甲基苯乙烯和β-CF3-1,3-烯炔。
所述草酸肟酯为苯乙醛酸肟酯、甲氧基乙醛酸肟酯、乙氧基乙醛酸肟酯。
本技术方案在可见光催化条件下,通过N-O键的均裂,产生的氮自由基和氧自由基进行反应,合成β-氨基酸酯和β-氨基酮衍生物。
这种方法简单、绿色,为合成β-氨基酸酯和β-氨基酮衍生物提供了一种新的、高效的合成策略。
具体实施方式
下面结合实例对本发明的内容进一步的阐述,但不是对本发明的限定。
实施例1:
分别将30mmol 2-氯-2-氧乙酸乙酯滴加到0℃下的20mmol二苯甲酮肟和30mmol吡啶在1M无水THF中的搅拌溶液中,在室温下将反应再搅拌1小时,之后,用EtOAc和洗涤盐水稀释反应混合物,用无水Na2SO4干燥有机层,并在真空中浓缩,残渣通过硅胶层析纯化,得到产率为82%的2a。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.57–7.60(m,2H),7.44–7.52(m,4H),7.37–7.41(m,4H),4.31(q,J=7.2Hz,2H),1.31(t,J=7.2Hz,1H)ppm;13C NMR(100MHz,Chloroform-d)δ167.3,157.3,156.3,134.1,131.6,131.5,130.3,129.4,129.3,128.6,128.3,63.2,13.9ppm;HRMS(ESI):C17H15NNaO4+[M+Na]+Calcd 320.0893,Found 320.0894。
实施例2:
2-((二苯基亚甲基)氨基)氧基)-2-氧乙酸甲酯(2b)的制备方法和产物表征:
分别将30mmol 2-氯-2-氧乙酸甲酯滴加到0℃下的20mmol二苯甲酮肟和30mmol,1.5当量吡啶在1M无水THF中的搅拌溶液中,在室温下将反应再搅拌1小时,之后,用EtOAc和洗涤盐水稀释反应混合物,用无水Na2SO4干燥有机层,并在真空中浓缩,残渣通过硅胶层析纯化,得到产率为86%的2b。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.56–7.59(m,2H),7.45–7.50(m,4H),7.37–7.40(m,4H),3.85(s,3H)ppm;13C NMR(100MHz,Chloroform-d)δ167.5,157.7,156.1,134.0,131.6,131.5,130.4,129.4,129.2,128.6,128.3,53.6ppm;HRMS(ESI):C16H13NNaO4+[M+Na]+Calcd 306.0737,Found 306.0738。
实施例3:
1-((二苯基亚甲基)氨基)氧基)-2-苯基乙烷-1,2-二酮(2c)的制备方法和产物表征:
分别将30mmol 2-氧代-2-苯乙酰氯滴加到0℃下的20mmol二苯甲酮肟和30mmol吡啶在1M无水THF中的搅拌溶液中,在室温下将反应再搅拌1小时,之后,用EtOAc和洗涤盐水稀释反应混合物,用无水Na2SO4干燥有机层,并在真空中浓缩,残渣通过硅胶层析纯化,得到产率为79%的2c。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.93–7.96(m,2H),7.61–7.66(m,1H),7.42–7.50(m,8H),7.32–7.39(m,4H)ppm;13C NMR(100MHz,Chloroform-d)δ186.1,166.7,163.5,135.1,134.0,132.5,131.6,131.5,130.3,129.80,129.2,129.2,128.6,128.4ppm;HRMS(ESI):C21H15NNaO3+[M+Na]+Calcd 352.0944,Found 352.0940。
实施例4:
3-((二苯基亚甲基)氨基)-3,3-二苯基丙酸乙酯(3a)的制备方法和产物表征:
将0.2mmol 1,1-二苯乙烯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为76%的3a。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.67–7.70(m,2H),7.28–7.37(m,7H),7.11–7.20(m,7H),7.06(t,J=7.6Hz,2H),6.59–6.62(m,2H),3.86(q,J=7.2Hz,2H),3.18(s,2H),0.93(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.3,167.8,148.9,141.9,138.5,130.0,128.5,128.3,128.0,127.8,127.7,127.6,127.4,127.3,126.3,125.8,67.3,60.2,45.1,13.9ppm;HRMS(ESI):C30H28NO2+[M+H]+Calcd 434.2115,Found 434.2114。
实施例5:
3-((二苯基亚甲基)氨基)-3-苯基-3-(对甲苯基)丙酸乙酯(3b)的制备方法和产物表征:
将0.2mmol 1-甲基-4-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为78%的3b。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.60–7.61(m,2H),7.27–7.30(m,1H),7.20–7.25(m,4H),7.04–7.12(m,6H),6.98(t,J=7.2Hz,2H),6.91(d,J=8.4Hz,2H),6.53–6.54(m,2H),3.79(q,J=7.2Hz,2H),3.08(s,2H),2.22(s,3H),0.86(t,J=7.2Hz,3H)ppm;13C NMR(150MHz,Chloroform-d)δ169.3,166.4,147.9,144.9,140.9,137.5,134.6,128.8,127.4,127.36,126.9,126.7,126.6,126.5,126.2,126.1,125.1,66.1,59.0,44.0,20.0,12.9ppm;HRMS(ESI):C31H30NO2+[M+H]+[M+Na]+Calcd 448.2271,Found 448.2273。
实施例6:
3-((二苯基亚甲基)氨基)-3-(4-甲氧基苯基)-3-苯基丙酸乙酯(3c)的制备方法和产物表征:
将0.2mmol 1-甲氧基-4-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为74%的3c。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.66–7.69(m,2H),7.29–7.36(m,5H),7.13–7.21(m,6H),7.06–7.10(m,2H),6.70–6.73(m,2H),6.61–6.63(m,2H),3.87(q,J=7.2Hz,2H),3.77(s,3H),0.94(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.3,167.5,157.9,149.1,141.9,141.1,138.6,129.9,128.8,128.4,127.9,127.8,127.7,127.6,127.4,127.3,126.2,113.1,66.9,60.1,55.3,45.3,14.0ppm;HRMS(ESI):C31H30NO2+[M+Na]+Calcd 461.0560,Found 461.0564。
实施例7:
3-((二苯基亚甲基)氨基)-3-(4-氟苯基)-3-苯基丙酸乙酯(3d)的制备方法和产物表征:
将0.2mmol 1-氟-4-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为78%的3d。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.66–7.68(m,2H),7.36–7.39(m,1H),7.29–7.32(m,4H),7.14–7.22(m,6H),7.08(t,J=7.8Hz,2H),6.88(t,J=9.0Hz,2H),6.22(d,J=7.2Hz,2H),3.87(q,J=7.2Hz,2H),3.13–3.19(m,2H),0.94(t,J=7.2Hz,3H)ppm;13C NMR(150MHz,Chloroform-d)δ170.1,167.9,161.3(d,1JC-F=243.6Hz),148.5,144.7(d,3JC-F=3.9Hz),141.7,138.4,130.0,129.3(d,3JC-F=7.7Hz),128.4,127.9,127.8,127.6,127.4,127.4,127.3,126.4,114.5,114.3,66.9,60.2,45.2,13.9ppm;HRMS(ESI):C30H27FNO2+[M+H]+Calcd 452.2020,Found 452.2038.
实施例8:
3-(4-氯苯基)-3-((二苯基亚甲基)氨基)-3-苯基丙酸乙酯(3e)的制备方法和产物表征:
将0.2mmol 1-氯-4-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为69%的3e。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.65–7.70(m,2H),7.36–7.39(m,1H),7.29–7.34(m,4H),7.14–7.22(m,8H),7.09(t,J=7.8Hz,2H),6.62(d,J=4.8Hz,2H),3.88(q,J=7.2Hz,2H),3.12–3.20(m,2H),0.95(t,J=7.2Hz,3H)ppm;13C NMR(150MHz,Chloroform-d)δ167.0,168.1,148.2,147.5,141.6,138.3,131.9,130.1,129.2,128.4,127.9,127.9,127.8,127.6,127.4,127.38,127.35,126.4,66.9,60.2,45.0,13.9ppm;HRMS(ESI):C30H27ClNO2+[M+H]+Calcd 468.1725,Found 461.1724。
实施例9:
3-((二苯基亚甲基)氨基)-3-苯基-3-(间甲苯基)丙酸乙酯(3f)的制备方法和产物表征:
将0.2mmol 1-甲基-3-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为71%的3f。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.67–7.70(m,2H),7.29–7.38(m,5H),7.14–7.22(m,4H),7.00–7.08(m,5H),6.93–6.95(m,1H),6.60(d,J=7.2Hz,2H),3.86(q,J=7.2Hz,2H),3.11–3.21(m,2H),2.21(s,3H),0.95(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.4,167.6,149.0,148.6,142.0,138.5,137.1,129.9,128.5,128.3,127.9,127.8,127.7,127.7,127.6,127.3,127.2,127.0,126.2,125.1,67.3,60.1,45.2,21.6,13.9ppm;HRMS(ESI):C31H30NO2+[M+H]+Calcd 448.2271,Found 448.2276。
实施例10:
3-((二苯基亚甲基)氨基)-3,3-二对甲苯基丙酸乙酯(3g)的制备方法和产物表征:
将0.2mmol 4,4’-(乙烯-1,1-二基)二(甲苯)、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为83%的3g。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.66–7.70(m,2H),7.27–7.36(m,3H),7.15–7.19(m,5H),7.05(t,J=7.6Hz,2H),6.97(d,J=7.6Hz,4H),6.62(d,J=7.2Hz,2H),3.87(q,J=7.2Hz,2H),3.13(s,2H),2.28(s,6H),0.94(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.5,167.3,146.1,142.0,138.7,135.6,129.9,128.5,128.5,127.9,127.6,127.6,127.3,127.2,67.0,60.1,45.2,21.1,14.0ppm;HRMS(ESI):C32H31NO2+[M+H]+Calcd 461.2355,Found 461.2389.
实施例11:
3,3-二(4-氯苯基)-3-((二苯基亚甲基)氨基)丙酸乙酯(3h)的制备方法和产物表征:
将0.2mmol 4,4’-(乙烯-1,1-二基)二(氯苯)、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中化合物被溶解,并用氩气回填三次在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为71%的3h。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.63–7.66(m,2H),7.30–7.40(m,3H),7.09–7.24(m,11H),6.63–6.65(m,2H),3.88(q,J=7.2Hz,2H),3.14(s,2H),2.28(s,6H),0.95(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ169.7,168.5,146.9,141.4,138.3,132.3,130.3,129.2,128.4,128.1,128.0,127.6,127.5,127.4,66.7,60.4,45.2,14.0ppm;HRMS(ESI):C30H26Cl2NO2+[M+H]+Calcd 502.1335,Found 502.1339。
实施例12:
3-((二苯基亚甲基)氨基)-3-(4-氟苯基)-3-(4-甲氧基苯基)丙酸乙酯(3i)的制备方法和产物表征:
将0.2mmol 1-氟-4-(1-(4-甲氧基苯基)乙烯基)苯0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为79%的3i。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.65–7.67(m,2H),7.29–7.38(m,5H),7.18–7.23(m,1H),7.08–7.12(m,4H),6.86–6.90(m,2H),6.68–6.72(m,2H),6.63(d,J=8.0Hz,2H),3.88(q,J=7.2Hz,2H),3.76(s,3H),3.09–3.17(m,2H),0.95(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.2,167.7,161.3(d,1JC-F=245.0Hz),158.1,145.0,144.98(d,3JC-F=3.0Hz),141.8,140.8,138.5,130.1,129.4(d,3JC-F=7.6Hz),128.7,128.4,128.0,127.5,127.4,127.3,114.4(d,2JC-F=21.2Hz),113.2,66.6,60.2,55.3,45.5,14.0ppm;HRMS(ESI):C31H29FNO3+[M+H]+Calcd 482.2126,Found 482.2123。
实施例13:
3-(3,4-二甲基苯基)-3-((二苯基亚甲基)氨基)-3-苯基丙酸乙酯(3j)的制备方法和产物表征:
将0.2mmol 1,2-二甲基-4-(1-苯基乙烯基)苯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填了三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为75%的3j。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.67–7.69(m,2H),7.29–7.38(m,5H),7.12–7.22(m,4H),7.03–7.07(m,2H),6.90–6.96(m,3H),6.58–6.61(m,2H),3.87(q,J=7.2Hz,2H),3.11–3.19(m,2H),2.19(s,3H),2.12(s,3H),0.93(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ170.4,167.3,149.1,146.0,142.0,138.6,135.6,134.4,129.9,129.0,128.9,128.4,127.9,127.7,127.6,127.2,127.1,126.1,125.2,67.1,60.1,45.2,20.0,19.4,13.9ppm;HRMS(ESI):C32H32NO2+[M+H]+Calcd 462.2428,Found 462.2428。
实施例14:
3-((二苯基亚甲基)氨基)-3-苯基丙酸乙酯(3k)的制备方法和产物表征:
将0.2mmol 1-苯基乙烯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填了三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为65%的3k。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.64–7.66(m,2H),7.26–7.43(m,9H),7.20–7.24(m,2H),7.03–7.07(m,2H),7.03–7.06(m,2H),4.87(dd,J=9.2,4.4Hz,1H),3.98–4.12(m,2H),3.06(dd,J=15.0,9.2Hz,1H),2.77(dd,J=15.0,4.4Hz,1H),1.16(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.5,168.3,143.7,139.9,136.8,130.1,129.4,128.8,128.6,128.5,128.4,128.1,128.0,127.9,127.8,127.1,126.7,63.1,60.3,44.6,14.3ppm;HRMS(ESI):C24H24NO2+[M+H]+Calcd 358.1802,Found 358.1799。
实施例15:
3-(4-叔丁基苯基)-3-((二苯基亚甲基)氨基)丙酸乙酯(3l)的制备方法和产物表征:
将0.2mmol 1-(4-(叔丁基)苯基)乙烯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为68%的3l。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.62–7.65(m,2H),7.40–7.43(m,3H),7.27–7.35(m,5H),7.19–7.21(m,2H),7.06–7.09(m,2H),4.85(dd,J=9.2,4.4Hz,1H),3.99–4.11(m,2H),3.05(dd,J=15.0,9.2Hz,1H),2.76(dd,J=15.0,4.6Hz,1H),1.30(s,9H),1.14(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.6,167.8,149.8,140.4,140.0,136.8,130.1,129.4,128.7,128.5,128.4,128.0,127.9,126.7,125.3,62.7,60.3,44.5,34.5,31.4,14.2ppm;HRMS(ESI):C28H32NO2+[M+H]+Calcd 414.2428,Found 414.2424.
实施例16:
3-((二苯基亚甲基)氨基)-3-(4-甲氧基苯基)丙酸乙酯(3m)的制备方法和产物表征:
将0.2mmol 1-(4-(甲氧基)苯基)乙烯、0.3mmol 2a、1mmol%[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)和4mL EtOAc添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为70%的3m。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.62–7.64(m,2H),7.38–7.43(m,3H),7.28–7.36(m,3H),7.16–7.19(m,2H),7.04–7.06(m,2H),6.80–6.83(m,2H),4.82(dd,J=9.2,4.8Hz,1H),3.99–4.12(m,2H),3.77(s,3H),3.03(dd,J=15.0,9.2Hz,1H),2.74(dd,J=15.0,4.8Hz,1H),1.16(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.5,167.9,158.6,140.0,136.8,135.9,130.0,128.7,128.5,128.2,128.1,128.0,127.9,127.5,127.3,113.8,62.4,60.3,55.2,44.6,14.3ppm;HRMS(ESI):C25H26NO3+[M+H]+Calcd388.1907,Found 388.1906.
实施例17:
3-(4-乙酰氧基苯基)-3-((二苯基亚甲基)氨基)丙酸乙酯(3n)的制备方法和产物表征:
将0.2mmol 4-乙酰氧基苯乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为73%的3n。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.62–7.65(m,2H),7.37–7.43(m,3H),7.25–7.37(m,5H),7.03–7.07(m,2H),6.98–7.02(m,2H),4.87(dd,J=9.2,4.6Hz,1H),3.99–4.11(m,2H),3.03(dd,J=15.0,9.2Hz,1H),2.75(dd,J=15.0,4.8Hz,1H),2.73(s,3H),1.15(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.3,169.6,168.4,149.6,141.2,139.8,136.6,130.2,128.7,128.6,128.3,128.1,128.0,127.8,121.5,62.5,60.4,44.6,21.2,14.2ppm;HRMS(ESI):C26H26NO4+[M+H]+Calcd 416.1856,Found 416.1858.
实施例18:
3-(3-氯苯基)-3-((二苯基亚甲基)氨基)丙酸乙酯(3o)的制备方法和产物表征:
将0.2mmol 3-氯苯乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为62%的3o。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.63–7.66(m,2H),7.28–7.44(m,7H),7.18–7.21(m,2H),7.10–7.13(m,1H),7.02–7.05(m,2H),4.83(dd,J=9.0,4.6Hz,1H),4.00–4.11(m,2H),3.01(dd,J=15.0,9.0Hz,1H),2.75(dd,J=15.0,4.8Hz,1H),2.73(s,3H),1.16(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.1,168.9,145.7,139.7,136.5,134.2,130.3,129.8,129.3,128.8,128.7,128.4,128.3,128.2,128.0,127.8,127.3,125.2,62.5,60.4,44.4,14.2ppm;HRMS(ESI):C24H23ClNO2+[M+H]+Calcd 392.1412,Found392.1412。
实施例19:
3-(4-氯苯基)-3-((二苯基亚甲基)氨基)丙酸乙酯(3p)的制备方法和产物表征:
将0.2mmol 4-氯苯乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为67%的3p。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.62–7.65(m,2H),7.29–7.42(m,6H),7.23–7.26(m,2H),7.18–7.20(m,2H),7.01–7.04(m,2H),4.84(dd,J=9.0,4.8Hz,1H),3.98–4.11(m,2H),3.01(dd,J=15.0,9.0Hz,1H),2.74(dd,J=15.0,4.8Hz,1H),2.73(s,3H),1.16(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.2,168.7,142.2,139.7,136.6,132.7,130.2,128.7,128.6,128.4,128.3,128.1,127.7,62.3,60.4,44.4,14.2ppm;HRMS(ESI):C24H23ClNO2+[M+H]+Calcd 392.1412,Found 392.1410。
实施例20:
3-((二苯基亚甲基)氨基)-3-(吡啶-2-基)丙酸乙酯(3q)的制备方法和产物表征:
将0.2mmol 2-乙烯基吡啶、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为66%的3q。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ8.51–8.53(m,1H),7.67–7.71(m,2H),7.60–7.64(m,1H),7.37–7.42(m,4H),7.31–7.35(m,3H),7.08–7.15(m,3H),5.07(dd,J=8.4,4.8Hz,1H),4.00–4.11(m,2H),3.00–3.12(m,2H),1.15(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.5,169.7,162.1,149.1,139.8,136.6,136.4,130.3,128.9,128.7,128.4,128.3,128.1,127.8,122.1,121.8,64.4,60.3,42.5,14.2ppm;HRMS(ESI):C23H23ClN2O2+[M+H]+Calcd 359.1754,Found 359.1756。
实施例21:
3-((二苯基亚甲基)氨基)-3-苯基丁酸乙酯(3r)的制备方法和产物表征:
将0.2mmol 1-甲基-1-苯基乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为79%的3r。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.57–7.59(m,2H),7.27–7.37(m,3H),7.14–7.20(m,6H),7.07(t,J=7.6Hz,2H),6.61(t,J=7.4Hz,2H),4.03(q,J=7.2Hz,2H),3.17(d,J=13.6Hz,1H),2.93(d,J=13.6Hz,1H),1.57(s,3H),1.12(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ171.3,166.7,148.2,141.5,138.6,129.8,128.4,128.3,127.9,127.8,127.5,127.3,126.4,126.4,62.9,60.0,52.1,25.5,14.2ppm;HRMS(ESI):C25H26NO2+[M+H]+Calcd 372.1958,Found 372.1967。
实施例22:
3-(4-氯苯基)-3-((二苯基亚甲基)氨基)丁酸乙酯(3s)的制备方法和产物表征:
将0.2mmol 1-甲基-1-(4-氯苯基)乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为77%的3s。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.50–7.51(m,2H),7.26–7.30(m,1H),7.20–7.24(m,2H),7.12–7.16(m,1H),7.01–7.07(m,6H),6.56(d,J=7.2Hz,2H),3.94(q,J=7.2Hz,2H),3.05(d,J=13.8Hz,1H),2.87(d,J=13.8Hz,1H),1.49(s,3H),1.05(t,J=7.2Hz,3H)ppm;13C NMR(100MHz,Chloroform-d)δ169.9,166.0,145.4,140.2,137.4,131.1,129.1,128.9,127.3,127.3,126.9,126.8,126.7,126.6,126.4,61.4,59.0,50.7,24.5,13.1ppm;HRMS(ESI):C25H25ClNO2+[M+H]+Calcd 406.1568,Found 406.1568。
实施例23:
3-([1,1'-联苯基]-4-基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟丁酸乙酯(3t)的制备方法和产物表征:
将0.2mmol 4-(3,3,3-三氟丙烷-1-烯-2-基)-1,1’-联苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为86%的3t。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.65–7.68(m,2H),7.58–7.61(m,2H),7.31–7.50(m,10H),7.17–7.21(m,1H),7.04(t,J=7.6Hz,2H),4.13(q,J=7.2Hz,2H),3.20(d,J=14.6Hz,1H),2.76(d,J=14.6Hz,1H),1.19(t,J=7.2Hz,3H)ppm;19F NMR(375MHz,Chloroform-d)δ-76.7ppm;13C NMR(100MHz,Chloroform-d)δ170.5,168.8,141.3,140.9,140.2,139.1,137.7,130.6,128.9,128.8,128.5,128.3,128.2,128.1,127.8,127.7,127.4,127.1,126.8,126.2(q,1JC-F=283.5Hz),67.9(q,2JC-F=25.8Hz),60.8,36.1,29.8,14.0ppm;HRMS(ESI):C31H27F3NO2+[M+H]+Calcd 502.1988,Found 502.1987。
实施例24:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(4-甲氧基苯基)丁酸乙酯(3u)的制备
方法和产物表征:
将0.2mmol 1-三氟甲基-1-(4-甲氧基苯基)乙烯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为82%的3u。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.63–7.64(m,2H),7.37–7.40(m,1H),7.30–7.33(m,2H),7.19–7.22(m,3H),7.07(t,J=7.8Hz,2H),6.77–6.80(m,2H),6.64–6.66(m,2H),4.11(q,J=7.2Hz,2H),3.80(s,3H),3.12(d,J=14.6Hz,1H),2.65(d,J=14.6Hz,1H),1.18(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-77.1ppm;13C NMR(150MHz,Chloroform-d)δ170.1,168.8,159.6,140.9,137.7,132.3,130.4,129.1,128.8,128.1,128.0,127.8,127.3,126.1(q,1JC-F=282.3Hz),113.5,67.6(q,2JC-F=26.0Hz),60.7,55.3,35.9,29.7,14.0ppm;HRMS(ESI):C26H25F3NO3+[M+H]+Calcd 456.1781,Found456.1782。
实施例25:
3-((二苯亚甲基)氨基)-4,4,4-三氟-3-(4-苯氧基苯酚)丁酸乙酯(3v)的制备方法和产物表征:
将0.2mmol 1-苯氧基-4-(3,3,3-三氟丙-1-烯-2-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为85%的3v。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.63–7.64(m,2H),7.30–7.40(m,5H),7.22–7.25(m,3H),7.10–7.14(m,3H),7.02(d,J=8.1Hz,2H),6.88(d,J=8.8Hz,2H),6.64–6.78(m,2H),4.12(q,J=7.2Hz,2H),3.14(d,J=14.5Hz,1H),2.71(d,J=14.5Hz,1H),1.18(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-76.8ppm;13C NMR(150MHz,Chloroform-d)δ170.4,168.7,157.5,156.6,140.8,137.7,134.6,130.5,129.9,129.5,128.8,128.3,128.2,128.0,127.8,127.4,126.3(q,1JC-F=285.4Hz),123.7,119.1,118.1,67.6(q,2JC-F=25.9Hz),60.8,36.1,29.7,14.0ppm;HRMS(ESI):C31H26F3NNaO3+[M+Na]+Calcd540.1757,Found 540.1776。
实施例26:
3-(4-乙酰基苯基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟丁酸乙酯(3w)的制备
方法和产物表征:
将0.2mmol 1-(4-(3,3,3-三氟丙基-1-烯-2-基)苯基)乙烷-1-酮、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为81%的3w.产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.89–7.91(m,1H),7.82–7.84(m,1H),7.62–7.65(m,3H),7.38–7.41(m,2H),7.30–7.33(m,2H),7.16–7.19(m,1H),7.01–7.05(m,2H),6.54–6.74(m,2H),4.12(q,J=7.2Hz,2H),3.23(d,J=14.6Hz,1H),2.82(d,J=14.6Hz,1H),2.53(s,3H),1.18(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-76.6ppm;13C NMR(150MHz,Chloroform-d)δ197.5,171.0,168.5,140.5,137.5,136.8,133.2,130.7,128.8,128.6,128.5,128.3,128.3,128.1,127.6,127.4,127.2,124.3(q,1JC-F=285.3Hz),68.0(q,2JC-F=25.9Hz),60.9,36.3,26.7,13.9ppm;HRMS(ESI):C27H24F3NNaO3+[M+Na]+Calcd490.1600,Found 490.1605。
实施例27:
4-(2-((二苯基亚甲基)氨基)-4-乙氧基-1,1,1-三氟-4-氧代丁烷-2-基)苯甲酸甲酯(3x)的制备方法和产物表征:
将0.2mmol 4-(3,3,3-三氟丙-1-烯-2-基)苯甲酸甲酯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为80%的3x。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.93–7.94(m,2H),7.63–7.65(m,2H),7.39–7.42(m,3H),7.32–7.35(m,2H),7.19–7.22(m,1H),7.04–7.08(m,2H),6.52–6.74(m,2H),4.12(q,J=7.2Hz,2H),3.92(s,3H),3.18(d,J=14.6Hz,1H),2.74(d,J=14.6Hz,1H),1.19(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-76.6ppm;13C NMR(150MHz,Chloroform-d)δ170.9,168.4,166.6,144.9,140.6,137.5,130.7,130.2,129.3,128.9,128.4,128.2,128.1,127.7,127.5,126.0(q,1JC-F=285.4Hz),68.0(q,2JC-F=25.8Hz),60.8,52.3,36.0,29.7,14.0ppm;HRMS(ESI):C27H25F3NO4+[M+H]+Calcd 484.1730,Found484.1730。
实施例28:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(4-氟苯基)丁酸乙酯(3y)的制备方法
和产物表征:
将0.2mmol 1-氟-4-(3,3,3-三氟丙基-1-烯-2-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为78%的3y。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.62–7.64(m,2H),7.39–7.41(m,1H),7.32–7.34(m,2H),7.28–7.30(m,2H),7.21–7.24(m,1H),7.09(t,J=7.7Hz,2H),6.95–6.98(m,2H),6.55–6.72(m,2H),4.12(q,J=7.2Hz,2H),3.12(d,J=14.6Hz,1H),2.70(d,J=14.6Hz,1H),1.19(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-77.0,-113.12–113.16(m)ppm;13C NMR(150MHz,Chloroform-d)δ170.6,168.5,162.6(d,1JC-F=249.3Hz),140.7,137.6,136.0,135.9,130.6,129.9(d,3JC-F=7.9Hz),128.8,128.3,128.0,127.6,127.4,126.2(q,1JC-F=284.9Hz),115.1(d,2JC-F=21.7Hz),67.6(q,2JC-F=26.1Hz),60.8,36.1,13.9ppm;HRMS(ESI):C25H22F4NO2+[M+H]+Calcd 444.1581,Found 444.1580。
实施例29:
3-(4-溴苯基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟丁酸乙酯(3z)的制备方法和产物表征:
将0.2mmol 1-溴-4-(3,3,3-三氟丙基-1-烯-2-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为79%的3z。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.62–7.64(m,2H),7.39–7.42(m,3H),7.32–7.34(m,2H),7.22–7.25(m,2H),7.18–7.20(m,1H),7.10(t,J=7.7Hz,2H),6.60–6.75(m,2H),4.11(q,J=7.2Hz,2H),3.11(d,J=14.9Hz,1H),2.69(d,J=14.9Hz,1H),1.18(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-76.9ppm;13C NMR(150MHz,Chloroform-d)δ170.8,168.5,140.6,139.1,137.5,131.3,130.7,129.8,128.9,128.4,128.3,128.1,127.7,127.5,126.0(q,1JC-F=284.8Hz),122.9,67.4(q,2JC-F=26.0Hz),60.9,36.0,14.0ppm HRMS(ESI):C25H22BrF3NO2+[M+H]+Calcd 504.0781,Found 504.0780。
实施例30:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(萘-2-基)丁酸乙酯(4a)的制备方法
和产物表征:
将0.2mmol 2-(3,3,3-三氟丙基-1-烯-2-基)萘、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为72%的4a。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.82(d,J=8.0Hz,1H),7.77(d,J=8.7Hz,1H),7.70(d,J=8.1Hz,1H),7.68–7.65(m,2H),7.62(d,J=2.0Hz,1H),7.56(d,J=8.8Hz,1H),7.46–7.53(m,2H),7.40–7.43(m,1H),7.32–7.35(m,2H),7.07–7.10(m,2H),6.87(s,2H),6.45–6.70(m,2H),4.14(q,J=7.2Hz,2H),3.32(d,J=14.6Hz,1H),2.83(d,J=14.6Hz,1H),1.21(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-76.5ppm;13C NMR(150MHz,Chloroform-d)δ170.6,168.8,140.9,137.5,137.4,132.9,132.6,130.6,128.9,128.4,128.3,128.2,128.0,127.9,127.7,127.4,127.2,126.9,126.8,126.3,126.0,126.0(q,1JC-F=285.3Hz),68.1(q,2JC-F=26.0Hz),60.8,36.1,29.7,14.0ppm HRMS(ESI):C29H25F3NO2+[M+H]+Calcd 476.1832,Found 476.1842。
实施例31:
3-(苯并[b]噻吩-3-基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟丁酸乙酯(4b)的制备方法和产物表征:
将0.2mmol 3-(3,3,3-三氟丙基-1-烯-2-基)苯并噻吩、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为69%的4b。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ8.08(d,J=8.3Hz,1H),7.81(d,J=8.1Hz,1H),7.64(dd,J=8.4,1.4Hz,2H),7.39–7.42(m,1H),7.29–7.34(m,4H),7.24–7.26(m,2H),7.14–7.17(m,1H),6.93–7.04(m,3H),4.17(q,J=7.2Hz,2H),3.24(d,J=13.8Hz,1H),2.83(d,J=13.8Hz,1H),1.21(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-75.5ppm;13C NMR(150MHz,Chloroform-d)δ170.6,168.5,140.2,140.1,137.9,136.8,134.4,130.6,128.7,128.2,128.0,127.2,126.8,126.7,126.4(q,1JC-F=284.6Hz),125.1,124.4,124.4,122.6,67.8(q,2JC-F=27.4Hz),60.9,38.1,29.7,13.9ppm HRMS(ESI):C27H23F3NO2S+[M+H]+Calcd 482.1396,Found 482.1395。
实施例32:
3-((二苯基亚甲基)氨基)-5-苯基-3-(三氟甲基)戊-4-炔酸乙酯(4c)的制备方法和产物表征:
将0.2mmol(3-(三氟甲基)丁-3-烯-1-炔-1-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为66%的4c.。
产物表征为:
1H NMR(600MHz,Chloroform-d)δ7.58–7.60(m,2H),7.35–7.40(m,3H),7.29–7.32(m,4H),7.22–7.25(m,2H),7.17–7.20(m,2H),7.03–7.04(m,2H),4.14(q,J=7.2Hz,2H),3.28(d,J=14.2Hz,1H),3.06(d,J=14.2Hz,1H),1.19(t,J=7.2Hz,3H)ppm;19F NMR(565MHz,Chloroform-d)δ-77.5ppm;13C NMR(150MHz,Chloroform-d)δ171.8,168.0,140.6,136.2,131.8,130.7,129.0,128.7,128.6,128.5,128.0,127.8,127.5,124.4(q,1JC-F=283.9Hz),121.9,91.2,82.6,63.4(q,2JC-F=28.4Hz),60.8,42.7,29.7,14.1ppm;HRMS(ESI):C27H23F3NO2+[M+H]+Calcd 450.1675,Found 450.1681。
实施例33:
3-((二苯基亚甲基)氨基)-5-(对甲苯基)-3-(三氟甲基)戊-4-炔酸乙酯(4d)的制备方法和产物表征:
将0.2mmol 1-甲基-4-(3-(三氟甲基)丁-3-烯-1-炔-1-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为70%的4d。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.57–7.60(m,2H),7.28–7.41(m,7H),7.22–7.25(m,1H),7.00(d,J=8.0Hz,2H),6.93(d,J=8.0Hz,2H),4.13(q,J=7.2Hz,2H),3.26(d,J=14.2Hz,1H),3.04(d,J=14.2Hz,1H),2.31(s,3H),1.18(t,J=7.2Hz,3H)ppm;19F NMR(375MHz,Chloroform-d)δ-77.6ppm;13C NMR(100MHz,Chloroform-d)δ171.8,168.1,140.7,138.7,136.3,132.5,131.7,130.7,130.1,129.4,129.0,128.7,128.6,128.3,128.1,128.0,127.9,127.5,118.9,91.3,81.9,63.4(q,2JC-F=28.4Hz),60.8,42.7,21.5,14.1ppm;HRMS(ESI):C28H25F3NO2+[M+H]+Calcd 464.1832,Found 464.1839。
实施例34:
3-((二苯基亚甲基)氨基)-5-(4-氟苯基)-3-(三氟甲基)戊-4-炔酸乙酯(4e)的制备方法和产物表征:
将0.2mmol 1-氟-4-(3-(三氟甲基)丁-3-烯-1-炔-1-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为68%的4e。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.56–7.59(m,2H),7.28–7.41(m,7H),7.21–7.25(m,1H),7.00–7.03(m,2H),6.86–6.91(m,2H),4.14(q,J=7.2Hz,2H),3.29(d,J=14.2Hz,1H),3.05(d,J=14.2Hz,1H),1.19(t,J=7.2Hz,3H)ppm;19F NMR(375MHz,Chloroform-d)δ-77.5,-110.39–110.42(m)ppm;13C NMR(100MHz,Chloroform-d)δ171.8,168.0,162.6(d,1JC-F=250.0Hz),140.6,136.3,133.8,133.7,130.8,129.0,128.7,128.6,128.0,127.5,115.1(d,2JC-F=22.1Hz),90.3,82.3,63.4(q,2JC-F=28.4Hz),60.9,42.8,14.2ppm;HRMS(ESI):C27H22F4NO2+[M+H]+Calcd 468.1581,Found 468.1588。
实施例35:
5-(3-氯苯基)-3-((二苯基亚甲基)氨基)-3-(三氟甲基)戊-4-炔酸乙酯(4f)的制
备方法和产物表征:
将0.2mmol 1-氯-3-(3-(三氟甲基)丁-3-烯-1-炔-1-基)苯、0.3mmol 2a、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为62%的4f。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.56–7.59(m,2H),7.46–7.49(m,1H),7.28–7.41(m,6H),7.21–7.24(m,1H),7.12(t,J=7.8Hz,2H),6.97(t,J=1.8Hz,2H),6.91–6.93(m,1H),4.15(q,J=7.2Hz,2H),3.31(d,J=14.2Hz,1H),3.06(d,J=14.2Hz,1H),1.20(t,J=7.2Hz,3H)ppm;19F NMR(375MHz,Chloroform-d)δ-77.4ppm;13C NMR(100MHz,Chloroform-d)δ172.0,167.9,159.0,140.5,138.2,136.2,135.5,133.6,131.8,130.8,130.1,129.9,129.6,129.4,129.1,129.0,128.9,128.8,128.7,128.6,128.3,128.1,127.9,127.6,124.3(q,1JC-F=282.9Hz),123.6,90.1,83.8,63.5(q,2JC-F=28.5Hz),60.9,42.8,14.2ppm;HRMS(ESI):C27H22ClF3NO2+[M+H]+Calcd 484.1286,Found 484.1291。
实施例36:
3-((二苯基亚甲基)氨基)-3,3-二苯基丙酸甲酯(4g)的制备方法和产物表征:
将0.2mmol 1,1-二苯乙烯、0.3mmol 2b(、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为81%的4g。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.67–7.69(m,2H),7.28–7.37(m,7H),7.14–7.21(m,7H),7.05–7.08(m,2H),6.58–6.61(m,2H),3.40(s,3H),3.19(s,2H),ppm;13C NMR(100MHz,Chloroform-d)δ170.7,167.8,148.8,141.9,138.5,130.0,128.5,128.0,127.8,127.7,127.5,127.4,127.3,126.3,67.3,51.4,44.9ppm;HRMS(ESI):C29H26NO2+[M+H]+Calcd 420.1958,Found 420.1957。
实施例37:
3-([1,1'-联苯基]-4-基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟丁酸甲酯(4h)的制备方法和产物表征:
将0.2mmol 4-(3,3,3-三氟丙烷-1-烯-2-基)-1,1’-联苯、0.3mmol 2b、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为83%的4h。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.64–7.67(m,2H),7.58–7.61(m,2H),7.31–7.51(m,10H),7.17–7.22(m,1H),7.05(t,J=7.6Hz,2H),6.62–6.76(m,2H),3.67(s,3H),3.21(d,J=14.6Hz,1H),2.75(d,J=14.6Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-76.9ppm;13C NMR(100MHz,Chloroform-d)δ170.7,169.3,141.3,140.9,140.2,139.0,137.7,130.6,128.9,128.9,128.4,128.2,128.1,127.8,127.7,127.4,127.1,126.8,126.4(q,1JC-F=285.4Hz),67.9(q,2JC-F=26.1Hz),52.0,35.6ppm;HRMS(ESI):C30H25F3NO2+[M+H]+Calcd 488.1832,Found 488.1832。
实施例38:
(R)-3-((二苯基亚甲基)氨基)-5-苯基-3-(三氟甲基)戊-4-炔酸甲酯(4i)的制备方法和产物表征:
将0.2mmol(3-(三氟甲基)丁-3-烯-1-炔-1-基)苯、0.3mmol 2b、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为70%的4i.
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.57–7.60(m,2H),7.27–7.41(m,8H),7.17–7.24(m,3H),7.02–7.05(m,2H),3.69(s,3H),3.31(d,J=14.4Hz,1H),3.08(d,J=14.4Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-77.6ppm;13C NMR(100MHz,Chloroform-d)δ172.0,168.5,140.6,136.2,131.8,130.8,129.0,128.7,128.6,128.5,128.1,127.8,127.5,124.4(q,1JC-F=284.2Hz),121.9,91.4,82.5,63.4(q,2JC-F=28.2Hz),52.0,42.5ppm;HRMS(ESI):C26H21F3NO2+[M+H]+Calcd 436.1519,Found 436.1520.
实施例39:
3-((二苯基亚甲基)氨基)-1-苯基-3-(吡啶-2-基)丙烷-1-酮(4j)的制备方法和产物表征:
将0.2mmol 2-乙烯基吡啶、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为67%的4j.
产物表征为:
1H NMR(400MHz,Chloroform-d)δ8.53–8.54(m,1H),7.93–7.95(m,2H),7.60–7.64(m,2H),7.47–7.52(m,1H),7.27–7.41(m,10H),7.06–7.15(m,3H),5.28(dd,J=8.0,4.8Hz,1H),3.72–3.83(m,2H)ppm;19F NMR(375MHz,Chloroform-d)δ-77.6ppm;13C NMR(100MHz,Chloroform-d)δ198.4,162.4,149.2,139.7,137.3,136.6,136.6,132.9,130.2,128.9,128.6,128.5,128.4,128.3,128.1,128.0,127.7,122.1,122.0,64.3,46.4ppm;HRMS(ESI):C27H23F3N2O+[M+H]+Calcd 391.1805,Found 391.1806。
实施例40:
3-([1,1'-联苯基]-4-基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟-1-苯基丁烷-1-酮(4k)的制备方法和产物表征:
将0.2mmol 4-(3,3,3-三氟丙烷-1-烯-2-基)-1,1’-联苯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为82%的4k。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.80–7.82(m,2H),7.71–7.74(m,2H),7.60–7.63(m,2H),7.53–7.57(m,4H),7.32–7.48(m,9H),7.08–7.12(m,1H),6.93(t,J=7.6Hz,2H),6.65–6.76(m,2H),4.11(d,J=16.6Hz,1H),3.15(d,J=16.6Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-75.4ppm;13C NMR(100MHz,Chloroform-d)δ194.3,169.6,141.1,141.0,140.3,140.1,138.0,137.7,133.0,130.6,129.7,129.4,129.0,128.9,128.7,128.5,128.4,128.2,128.1,128.0,127.9,127.8,127.7,127.5,127.2,126.9,126.5(q,1JC-F=284.9Hz),68.4(q,2JC-F=25.9Hz),38.6ppm;HRMS(ESI):C35H27F3NO+[M+H]+Calcd534.2039,Found 534.2037。
实施例41:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(4-甲氧基苯基)-1-苯基丁烷-1-酮(4l)的制备方法和产物表征:
将0.2mmol 1-三氟甲基-1-(4-甲氧基苯基)乙烯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为76%的4l。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.76–7.79(m,2H),7.68–7.71(m,2H),7.49–7.57(m,1H),7.32–7.44(m,7H),7.09–7.13(m,1H),6.93–6.97(m,2H),6.83–6.87(m,2H),6.62–6.73(m,2H),4.05(d,J=16.6Hz,1H),3.83(s,3H),3.02(d,J=16.6Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-75.9ppm;13C NMR(100MHz,Chloroform-d)δ194.3,169.2,159.5,141.1,138.1,137.7,133.3,132.9,130.4,129.3,129.1,128.9,128.5,128.5,128.4,128.1,128.0,127.9,127.8,127.4,126.4(q,1JC-F=284.7Hz),113.4,68.0(q,2JC-F=25.8Hz),55.3,38.4ppm;HRMS(ESI):C30H25F3NO2+[M+H]+Calcd 488.1832,Found488.1833。
实施例42:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(4-苯氧基苯酚)-1-苯基丁烷-1-酮(4m)的制备方法和产物表征:
将0.2mmol 1-苯氧基-4-(3,3,3-三氟丙-1-烯-2-基)苯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mLSchlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为78%的4m。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.77–7.79(m,2H),7.68–7.71(m,2H),7.50–7.54(m,1H),7.31–7.44(m,9H),7.11–7.16(m,2H),6.93–7.07(m,6H),6.65–6.79(m,2H),4.05(d,J=16.6Hz,1H),3.83(s,3H),3.02(d,J=16.6Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-75.7ppm;13C NMR(100MHz,Chloroform-d)δ194.3,169.5,157.4,156.7,141.0,138.1,137.6,135.6,133.0,130.5,129.9,129.5,128.9,128.5,128.2,128.1,128.0,127.8,127.5,126.5(q,1JC-F=284.8Hz),123.7,119.2,118.2,68.2(q,2JC-F=25.8Hz),38.5ppm;HRMS(ESI):C35H27F3NO2+[M+H]+Calcd 550.1988,Found 550.1990。
实施例43:
4-(2-((二苯基亚甲基)氨基)-1,1,1-三氟-4-氧代-4-苯基丁-2-基)苯甲酸甲酯(4n)的制备方法和产物表征:
将0.2mmol 4-(3,3,3-三氟丙-1-烯-2-基)苯甲酸甲酯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为79%的4n.
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.99–8.02(m,2H),7.73–7.76(m,2H),7.69–7.72(m,2H),7.63(d,J=8.2Hz,2H),7.50–7.54(m,1H),7.32–7.44(m,5H),7.08–7.12(m,1H),6.64(t,J=7.6Hz,2H),6.62–6.78(m,2H),4.06(d,J=16.9Hz,1H),3.93(s,3H),3.20(d,J=16.9Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-75.2ppm;13C NMR(100MHz,Chloroform-d)δ193.9,169.8,166.7,145.9,140.9,137.8,137.4,133.1,130.7,130.0,129.4,129.0,128.5,128.3,128.1,127.9,127.8,127.7,126.1(q,1JC-F=285.7Hz),68.6(q,2JC-F=25.9Hz),52.3,38.7ppm;HRMS(ESI):C31H25F3NO3+[M+H]+Calcd 516.1781,Found 516.1775.
实施例44:
3-((二苯基亚甲基)氨基)-4,4,4-三氟-3-(4-氟苯基)-1-苯基丁烷-1-酮(4o)的制备方法和产物表征:
将0.2mmol 1-氟-4-(3,3,3-三氟丙基-1-烯-2-基)苯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为75%的4o。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.75–7.77(m,2H),7.68–7.71(m,2H),7.46–7.54(m,4H),7.27–7.43(m,9H),7.10–7.14(m,1H),6.95–7.04(m,4H),6.63–6.76(m,2H),4.03(d,J=16.7Hz,1H),3.12(d,J=16.7Hz,1H)ppm;19F NMR(375MHz,Chloroform-d)δ-75.7,-113.5ppm;13C NMR(100MHz,Chloroform-d)δ194.1,169.6,162.6(d,1JC-F=248.6Hz),159.0,140.9,138.2,137.9,137.5,136.9(d,4JC-F=3.3Hz),135.6,133.1,130.6,129.8(d,3JC-F=8.0Hz),130.0,129.4,129.0,128.7,128.5,128.2,128.1,128.0,127.9,127.7,127.6,127.5,126.2(q,1JC-F=284.6Hz),115.2(d,2JC-F=21.3Hz),68.1(q,2JC-F=26.0Hz),52.3,38.7ppm;HRMS(ESI):C29H22F4NO+[M+H]+Calcd 476.1632,Found476.1633。
实施例45:
3-(4-溴苯基)-3-((二苯基亚甲基)氨基)-4,4,4-三氟-1-苯基丁-1-酮(4p)的制备方法和产物表征:
将0.2mmol 1-溴-4-(3,3,3-三氟丙基-1-烯-2-基)苯、0.3mmol 2c、[Ir(dF(CF3)ppy)2(dtbbpy)](PF6)(1mmol%)和EtOAc(4mL)添加到配备有磁性搅拌棒的15mL Schlenk烧瓶中,化合物被溶解,并用氩气回填三次,在室温下,在距离约3cm 30W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法(PE-PE/EtOAc=1:9至1:4)纯化残余物,获得产率为77%的4p。
产物表征为:
1H NMR(400MHz,Chloroform-d)δ7.72–7.74(m,2H),7.67–7.69(m,2H),7.26–7.54(m,10H),7.10–7.14(m,1H),6.98(t,J=7.6 Hz,1H),6.62–6.78(m,2H),3.99(d,J=16.9Hz,1H),3.15(d,J=16.9 Hz,1H)ppm;19F NMR(375 MHz,Chloroform-d)δ-75.4 ppm;13CNMR(100 MHz,Chloroform-d)δ193.9,169.7,159.1,140.9,140.1,138.2,137.8,137.4,135.5,133.1,131.4,130.7,129.7,129.4,129.0,128.8,128.5,128.3,128.1,127.9,127.6,126.2(q,1JC-F=284.6 Hz),122.7,68.3(q,2JC-F=25.6 Hz),38.6 ppm;HRMS(ESI):C29H22BrF3NO+[M+H]+Calcd 536.0831,Found 536.083。
Claims (4)
2.根据权利要求1所述的基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法,其特征在于,合成β-氨基酸酯/β-氨基酮衍生物过程为:
将0.2 mmol,普通芳烃、0.3 mmol草酸肟酯、1 mmol% [Ir (dF (CF3) ppy)2 (dtbbpy)](PF6)和4 mL EtOAc添加到配备有磁性搅拌棒的15 mL Schlenk烧瓶中,化合物被溶解、并用氩气回填三次,在室温下,在距离约3 cm 30 W蓝色LED的照射下,将支口管旋盖并搅拌12h,在减压下去除溶剂,然后通过快速柱色谱法纯化残余物,获得β-氨基酸酯和β-氨基酮衍生物,其中,快速柱色谱法中PE-PE/EtOAc=1:9至1:4。
3.根据权利要求2所述的基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法,其特征在于,所述普通芳烃为二苯基烯烃、单苯基烯烃、α-三氟甲基苯乙烯和β-CF3-1,3-烯炔。
4.根据权利要求2所述的基于烯烃的自由基烷氧羰基化/羰基化反应获得β-氨基酸酯/β-氨基酮衍生物的方法,其特征在于,所述草酸肟酯为苯乙醛酸肟酯、甲氧基乙醛酸肟酯、乙氧基乙醛酸肟酯。
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