CN112778238B - 从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法 - Google Patents

从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法 Download PDF

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CN112778238B
CN112778238B CN202011635404.XA CN202011635404A CN112778238B CN 112778238 B CN112778238 B CN 112778238B CN 202011635404 A CN202011635404 A CN 202011635404A CN 112778238 B CN112778238 B CN 112778238B
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赵剑楠
苏俊琪
莫佳男
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Abstract

本发明涉及一种从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，属于化学领域。该方法为：以R取代的羧酸和R1'、R2'取代的胺类为原料，三苯基膦为脱氧剂，在二氯甲烷中，惰性气氛下，并在蓝光照射下，以[Ir(dF(CF3)ppy)2(dtbbpy)]PF6为光催化剂，Co(dmgH)(dmgH2)Cl2为金属配合物催化剂，反应得到酰胺类化合物；所述R为芳基、杂芳基、被保护的氨基、取代的烷基、取代的芳基或取代的被保护的氨基；所述R1'为氢基、取代的烷基、苯基或取代的苯基；所述R2'为氢基、取代的烷基、苯基或取代的苯基。

Description

从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的 方法
技术领域
本发明涉及一种从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，属于化学领域。
背景技术
酰胺键在生物系统的构建和组成中起着重要的作用，它是将氨基酸模板连接在一起形成蛋白质的主要化学键。酰胺键不仅存在于生物系统中，还存在于大量分子中，特别是已上市的主要药物。调查显示，在上市的药物中，含有酰胺键结构的多达25％。2006年，在对三家全球领先的制药公司的候选药物调查中，三分之二的药物都含有酰胺结构。并且据估算，所有参与现代医药的合成反应中16％是酰胺化反应，这使得酰胺化反应在制药领域变得普遍且重要。基于酰胺键的聚合物也有广泛的应用，例如日常材料如尼龙，或更先进的药物传递系统、粘合剂和伤口愈合材料等。此外，酰胺键通常也是农用化学品和精细化工产品中的关键结构元素。(Chem.Soc.Rev.2014,43,2714-2742)
在形式上，酰胺键是通过羧酸和胺的缩合，并脱去一当量水形成的。当胺和羧酸混合时，因为竞争的酸碱反应使得这个缩合反应是具有挑战性的。虽然相应的羧酸铵盐经加热可以形成酰胺键，但该制备价值有限。此外，羧酸与胺直接偶联的高活化位垒只能通过较苛刻的反应条件来克服。为了避免这些问题，酰胺键通常是通过活化的羧酸形成的。羧酸的活化一般是在碱及偶联剂的存在下实现的。虽然偶联剂的使用能使反应条件变得温和并有良好的产率，但需要多种化学计量数的试剂。因此，每形成一分子产物，将产生一个等量以上的副产物，从而降低了整体的原子经济性。除了偶联剂本身的成本和毒性之外，从反应混合物中去除这些副产物也是一个冗长和昂贵的过程。目前，许多利用醇类、醛类、腈和芳基卤化物等原料催化合成酰胺的方法已经被开发出来(Chem.Soc.Rev.2011,40,3405-3415)。以羧酸为起始原料催化合成酰胺在肽合成等方面具有很高的价值，然而在这方面的研究相对较少。近年来，低反应活性羧酸的直接催化酰胺化反应越来越受到人们的关注，越来越多的研究团队关注这一领域。因此采用一种条件温和的光催化与金属配合物催化协同催化的途径，以稳定易得的羧酸和胺为原料，实现酰胺化合物的高效制备，在制药科学、精细化工和材料科学等领域均有较理想的应用前景。
发明内容
本发明通过新的方法，解决了上述的问题。
本发明提供了一种从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，所述方法为：以R取代的羧酸和R1'、R2'取代的胺类为原料，三苯基膦为脱氧剂，在二氯甲烷中，惰性气氛下，并在蓝光照射下，以[Ir(dF(CF3)ppy)2(dtbbpy)]PF6为光催化剂，Co(dmgH)(dmgH2)Cl2为金属配合物催化剂，反应得到酰胺类化合物；所述R为芳基、杂芳基、被保护的氨基、取代的烷基、取代的芳基或取代的被保护的氨基；所述R1'为氢基、取代的烷基、苯基或取代的苯基；所述R2'为氢基、取代的烷基、苯基或取代的苯基。
本发明所述光催化剂[Ir(dF(CF3)ppy)2(dtbbpy)]PF6和金属配合物催化剂Co(dmgH)(dmgH2)Cl2的结构如下：
Figure BDA0002881008670000021
本发明所述方法的合成路线如下：
Figure BDA0002881008670000022
本发明优选为所述羧酸为
Figure BDA0002881008670000023
Figure BDA0002881008670000024
Figure BDA0002881008670000031
Figure BDA0002881008670000032
等。
本发明优选为所述胺类为NH3·H2O(wt 25％)、
Figure BDA0002881008670000033
Bn-NH2、
Figure BDA0002881008670000034
Figure BDA0002881008670000035
Figure BDA0002881008670000036
等。
本发明优选为所述R为C1-C6的直链烷基、C1-C6的环状烷基、苯基、萘基、被保护的氨基、呋喃基、吡啶基、取代的苯基、取代的被保护的氨基。
本发明优选为所述R1'为氢基、C1-C6的直链烷基、C1-C6的环状烷基、炔丙基、苄基、羧基、酯基、取代的苄基、取代的羧基、取代的酯基、苯基或取代的苯基。
本发明优选为所述R2'为氢基、C1-C6的直链烷基、C1-C6的环状烷基、炔丙基、苄基、羧基、酯基、取代的苄基、取代的羧基、取代的酯基、苯基或取代的苯基。
本发明优选为所述羧酸与胺类的物质的量比为1：1.5-2.0。
本发明优选为所述羧酸与三苯基膦的物质的量比为1：1.0-1.5。
本发明优选为所述光催化剂的用量为羧酸物质的量的1-3％。
本发明优选为所述金属配合物催化剂的用量为羧酸物质的量的5-10％。
本发明优选为所述反应的条件为：室温反应3-18h，搅拌速度为1200-1500r/min。
本发明有益效果为：
本发明所述方法通过光催化剂与金属配合物在光照条件下协同催化，利用膦自由基化学，在条件温和，操作简便的步骤下，直接从廉价、易得、种类丰富的羧酸和胺为原料，并且避免了使用有害的化学计量偶联试剂，可以实现相应酰胺类化合物的高效制备，模板反应扩大至克级反应，也有较好的收率，展现出很好的化学选择性和官能团容忍度，满足绿色化学要求。另外，天然氨基酸也能很好的适应该方法得到肽产物，为多肽的合成提供了新的途径。同时，利用该方法也能很方便地对复杂的药物分子和化合物进行后期修饰，对药物的衍生化研究有重大意义。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
先称取
Figure BDA0002881008670000041
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000042
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000043
33.0mg，产率86％。1H NMR(400MHz,CDCl3)δ7.56–7.26(m,5H),3.99–2.97(m,8H).13C NMR(100MHz,CDCl3)δ170.2,135.3,129.7,128.4,127.0,66.7.HRMS-ESI:calcd for C11H14NO2 +([M+H+])m/z 192.1019,found 192.1021.
实施例2
先称取
Figure BDA0002881008670000044
(977.0mg,8mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(93.3mg,0.08mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(144.4mg,0.4mmol)加入到圆底烧瓶中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(240.0mL)，再慢慢加入
Figure BDA0002881008670000045
(1045.4μL,12mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000046
1.2734g，产率83％。1H NMR(400MHz,CDCl3)δ7.56–7.26(m,5H),3.99–2.97(m,8H).13C NMR(100MHz,CDCl3)δ170.2,135.3,129.7,128.4,127.0,66.7.HRMS-ESI:calcd for C11H14NO2 +([M+H+])m/z 192.1019,found 192.1021.
实施例3
先称取
Figure BDA0002881008670000051
(30.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000052
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000053
31.7mg，产率72％。1H NMR(400MHz,CDCl3)δ7.39–7.32(m,1H),7.25(dd,J＝8.0,4.0Hz,1H),7.00(t,J＝8.0Hz,1H),6.91(d,J＝8.0Hz,1H),3.84(s,3H),3.83–3.45(m,6H),3.38–3.13(m,2H).13C NMR(100MHz,CDCl3)δ167.9,155.2,130.6,128.1,125.3,121.0,110.9,66.9,66.8,55.5,47.3,42.1.HRMS-ESI:calcd for C12H16NO3 +([M+H+])m/z 222.1125,found 222.1125.
实施例4
先称取
Figure BDA0002881008670000054
(30.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000055
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000056
38.0mg，产率86％。1H NMR(400MHz,CDCl3)δ7.31(t,J＝8.0Hz,1H),6.95(d,J＝8.0Hz,3H),3.82(s,3H),3.81–2.92(m,8H).13C NMR(100MHz,CDCl3)δ170.1,159.7,136.5,129.6,119.0,115.6,112.5,66.8,55.3,48.1,42.5.HRMS-ESI:calcd for C12H16NO3 +([M+H+])m/z 222.1125,found 222.1126.
实施例5
先称取
Figure BDA0002881008670000061
(27.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000062
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000063
34.7mg，产率85％。1H NMR(400MHz,CDCl3)δ7.30(d,J＝8.0Hz,1H),7.23(d,J＝4.0Hz,2H),7.17(d,J＝8.0Hz,1H),4.59–2.76(m,8H),2.37(s,3H).13C NMR(100MHz,CDCl3)δ169.6,137.5,134.2,129.5,127.3,126.6,122.9,65.9,20.3.HRMS-ESI:calcd for C12H16NO2 +([M+H+])m/z 206.1176,found 206.1165.
实施例6
先称取
Figure BDA0002881008670000064
(27.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000065
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000066
39.4mg，产率96％。1H NMR(400MHz,CDCl3)δ7.31(d,J＝8.0Hz,2H),7.21(d,J＝8.0Hz,2H),4.28–3.07(m,8H),2.38(s,3H).13C NMR(100MHz,CDCl3)δ170.6,140.1,132.3,129.1,127.2,66.9,21.4.HRMS-ESI:calcd for C12H16NO2 +([M+H+])m/z 206.1176,found 206.1173.
实施例7
先称取
Figure BDA0002881008670000067
(39.6mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000071
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000072
37.1mg，产率70％。1H NMR(400MHz,CDCl3)δ7.63(d,J＝8.0Hz,2H),7.59(d,J＝4.0Hz,2H),7.47(dd,J＝8.0,8.0Hz,4H),7.38(t,J＝4.0Hz,1H),4.24–3.08(m,8H).13C NMR(100MHz,CDCl3)δ170.3,142.8,140.1,134.0,128.9,127.8,127.7,127.2,127.1,66.94.HRMS-ESI:calcd for C17H18NO2 +([M+H+])m/z 268.1332,found268.1332.
实施例8
先称取
Figure BDA0002881008670000073
(40.2mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000074
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000075
40.9mg，产率76％。1H NMR(400MHz,CDCl3)δ7.56(s,2H),7.30(d,J＝12.0Hz,2H),4.28–3.06(m,8H).13C NMR(100MHz,CDCl3)δ167.6,136.2,131.9,129.1,129.1,124.5,121.7,65.8.HRMS-ESI:calcd for C11H13 78.9183BrNO2 +([M+H+])m/z 270.0124,found 270.0124.
实施例9
先称取
Figure BDA0002881008670000076
(40.2mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000081
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000082
42.1mg，产率78％。1H NMR(400MHz,CDCl3)δ7.56(d,J＝8.0Hz,2H),7.29(d,J＝8.0Hz,2H),4.24–2.98(m,8H).13C NMR(100MHz,CDCl3)δ169.4,134.1,131.8,128.8,124.2,66.8.HRMS-ESI:calcd for C11H13 78.9183BrNO2 +([M+H+])m/z270.0124,found 270.0122.
实施例10
先称取
Figure BDA0002881008670000083
(31.3mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000084
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应3h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000085
38.4mg，产率85％。1H NMR(400MHz,CDCl3)δ8.08–7.31(m,4H),4.63–2.82(m,8H).13C NMR(100MHz,CDCl3)δ168.3,135.0,132.6,127.8,127.6,65.8.HRMS-ESI:calcd for C11H13 34.9689ClNO2 +([M+H+])m/z 226.0629,found 226.0629.
实施例11
先称取
Figure BDA0002881008670000086
(38.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000087
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000091
40.4mg，产率78％。1H NMR(400MHz,CDCl3)δ7.69(d,J＝8.0Hz,2H),7.53(d,J＝8.0Hz,2H),4.16–2.98(m,8H).13C NMR(100MHz,CDCl3)δ168.9,138.9,132.0,131.7,127.4,125.7(d,J＝4.0Hz),125.0,66.8,48.0,42.5.HRMS-ESI:calcdfor C12H13F3NO2 +([M+H+])m/z 260.0893,found 260.0894.
实施例12
先称取
Figure BDA0002881008670000092
(36.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000093
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000094
41.5mg，产率83％。1H NMR(400MHz,CDCl3)δ8.09(d,J＝8.0Hz,2H),7.48(d,J＝8.0Hz,2H),3.94(s,3H),3.87–3.15(m,8H).13C NMR(100MHz,CDCl3)δ169.3,166.2,139.6,131.3,129.9,127.0,66.8,52.3.HRMS-ESI:calcd forC13H16NO4 +([M+H+])m/z 250.1074,found 250.1073.
实施例13
先称取
Figure BDA0002881008670000095
(62.3mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000096
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000101
63.7mg，产率74％。1H NMR(400MHz,CDCl3)δ7.42(d,J＝8.0Hz,2H),7.36(d,J＝12.0Hz,2H),6.88(s,1H),3.90–3.38(m,8H),1.52(s,9H).13C NMR(100MHz,CDCl3)δ170.2,152.5,140.2,129.3,128.4,118.0,80.9,66.8,28.3.HRMS-ESI:calcd for C16H23N2O4 +([M+H+])m/z 307.1652,found 307.1651.
实施例14
先称取
Figure BDA0002881008670000102
(49.6mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000103
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000104
37.2mg，产率59％。1H NMR(400MHz,CDCl3)δ7.85(d,J＝8.0Hz,2H),7.39(d,J＝8.0Hz,2H),3.99–3.22(m,8H),1.35(s,12H).13C NMR(100MHz,CDCl3)δ170.3,137.8,134.9,126.2,84.0,66.8,24.8.HRMS-ESI:calcd for C17H25NBO4 +([M+H+])m/z 318.1871,found 318.1877.
实施例15
先称取
Figure BDA0002881008670000105
(34.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000106
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000111
54.6mg，产率86％。1H NMR(400MHz,CDCl3)δ7.87(t,J＝8.0Hz,3H),7.63–7.47(m,3H),7.42(d,J＝8.0Hz,1H),4.17–3.96(m,1H),3.94–3.72(m,3H),3.65–3.40(m,2H),3.33–3.06(m,2H).13C NMR(100MHz,CDCl3)δ169.5,133.6,133.5,129.5,129.3,128.5,127.1,126.5,125.1,124.6,123.5,67.1,67.0,47.6,42.2.HRMS-ESI:calcd for C15H16NO2 +([M+H+])m/z 242.1176,found 242.1182.
实施例16
先称取
Figure BDA0002881008670000112
(22.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000113
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000114
28.5mg，产率75％。1H NMR(400MHz,CDCl3)δ7.49(s,1H),7.03(s,1H),6.49(s,1H),4.27–3.27(m,8H).13C NMR(100MHz,CDCl3)δ159.1,147.7,143.7,116.7,111.3,66.9.HRMS-ESI:calcd for C9H12NO3 +([M+H+])m/z 182.0812,found182.0811.
实施例17
先称取
Figure BDA0002881008670000115
(24.6mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000116
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000117
36.7mg，产率95％。1H NMR(400MHz,CDCl3)δ8.58(s,1H),7.81(t,J＝8.0Hz,1H),7.68(d,J＝4.0Hz,1H),7.35(s,1H),4.30–3.25(m,8H).13C NMR(100MHz,CDCl3)δ166.4,152.6,147.2,136.1,123.6,123.1,65.8,46.7,41.8,28.6.HRMS-ESI:calcd for C10H13N2O2 +([M+H+])m/z 193.0972,found 193.0972.
实施例18
先称取
Figure BDA0002881008670000121
(30.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000122
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000123
35.3mg，产率80％。1H NMR(400MHz,CDCl3)δ7.39–7.24(m,2H),7.24–7.12(m,3H),3.60(s,4H),3.54–3.42(m,2H),3.41–3.21(m,2H),3.04–2.89(m,2H),2.68–2.51(m,2H).13C NMR(100MHz,CDCl3)δ170.8,141.0,128.5,128.4,126.2,66.8,66.4,45.9,41.9,34.7,31.4.HRMS-ESI:calcd for C13H18NO2 +([M+H+])m/z 220.1332,found 220.1339.
实施例19
先称取
Figure BDA0002881008670000124
(25.6mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000125
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应6h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000126
19.7mg，产率50％。1H NMR(400MHz,CDCl3)δ3.92–3.24(m,8H),2.43(tt,J＝12.0,4.0Hz,1H),1.94–1.75(m,2H),1.74–1.64(m,3H),1.61–1.41(m,2H),1.36–1.16(m,3H).13C NMR(100MHz,CDCl3)δ174.7,67.0,45.9,41.9,40.2,29.3,25.8.HRMS-ESI:calcd for C11H20NO2 +([M+H+])m/z 198.1489,found 198.1495.
实施例20
先称取
Figure BDA0002881008670000131
(32.8mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000132
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000133
36.7mg，产率79％。1H NMR(400MHz,CDCl3)δ7.34(t,J＝8.0Hz,2H),7.23(d,J＝4.0Hz,3H),4.20–2.52(m,8H),1.54(s,6H).13C NMR(100MHz,CDCl3)δ174.0,145.1,127.95,125.5,123.7,65.2,45.9,27.2,25.3.HRMS-ESI:calcd forC14H20NO2 +([M+H+])m/z 234.1498,found 234.1490.
实施例21
先称取
Figure BDA0002881008670000134
(67.9mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000135
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000136
66.9mg，产率82％。1H NMR(400MHz,CDCl3)δ7.76(d,J＝8.0Hz,2H),7.60(d,J＝8.0Hz,2H),7.39(t,J＝8.0Hz,2H),7.31(t,J＝8.0Hz,2H),5.69(d,J＝8.0Hz,1H),4.50(dd,J＝8.0,8.0Hz,1H),4.41(dd,J＝8.0,4.0Hz,1H),4.33(dd,J＝4.0,8.0Hz,1H),4.21(t,J＝8.0,4.0Hz,1H),3.90–3.29(m,8H),1.97(dq,J＝4.0,8.0Hz,1H),0.95(dd,J＝8.0,8.0Hz,6H).13C NMR(100MHz,CDCl3)δ170.4,156.4,143.9,143.8,141.3,127.7,127.0,125.1,125.1,120.0,67.0,66.8,66.6,55.2,47.2,46.3,42.4,31.6,19.6,17.3.HRMS-ESI:calcd for C24H28N2NaO4 +([M+H+])m/z 431.1941,found 431.1947.
实施例22
先称取
Figure BDA0002881008670000141
(41.3mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000142
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000143
28.8mg，产率52％。1H NMR(400MHz,CDCl3)δ7.10(q,J＝8.0Hz,4H),3.80(dd,J＝8.0,4.0Hz,2H),3.72–3.59(m,1H),3.58–3.42(m,3H),3.42–3.22(m,2H),3.16–2.99(m,1H),2.44(d,J＝8.0Hz,2H),1.91–1.78(m,1H),1.44(d,J＝8.0Hz,3H),0.88(d,J＝8.0Hz,6H).13C NMR(100MHz,CDCl3)δ172.3,140.3,139.0,129.6,126.8,66.8,66.2,46.0,44.9,42.9,42.3,30.1,22.3,20.6.HRMS-ESI:calcd for C17H26NO2 +([M+H+])m/z 276.1958,found 276.1980.
实施例23
先称取
Figure BDA0002881008670000144
(46.0mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000145
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000146
19.3mg，产率32％。1H NMR(400MHz,CDCl3)δ7.70(dd,J＝8.0,4.0Hz,2H),7.59(s,1H),7.33(dd,J＝8.0,4.0Hz,1H),7.20–7.02(m,2H),3.97(q,J＝8.0Hz,1H),3.91(s,3H),3.85–3.73(m,1H),3.71–3.61(m,1H),3.59–3.49(m,2H),3.48–3.37(m,2H),3.36–3.22(m,1H),3.15–2.97(m,1H),1.52(d,J＝4.0Hz,3H).13CNMR(100MHz,CDCl3)δ172.3,157.6,136.9,133.4,129.1,129.1,127.6,125.9,125.4,119.1,105.6,66.8,66.3,55.3,46.0,43.1,42.4,20.7.HRMS-ESI:calcd for C18H21NNaO3 +([M+Na+])m/z 322.1414,found 322.1415.
实施例24
先称取
Figure BDA0002881008670000151
(57.1mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000152
(26.1μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000153
46.2mg，产率65％。1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.0Hz,2H),7.53(d,J＝12.0Hz,2H),4.09–3.22(m,8H),3.18–2.93(m,4H),1.57(dd,J＝8.0,8.0Hz,4H),0.88(t,J＝8.0Hz,6H).13C NMR(100MHz,CDCl3)δ168.8,141.6,139.0,127.6,127.4,66.8,50.1,22.1,11.1.HRMS-ESI:calcd for C17H27N2O4S+([M+H+])m/z355.1686,found 355.1691.
实施例25
先称取
Figure BDA0002881008670000154
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入Bn-NH2(32.8μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000155
24.1mg，产率51％。1H NMR(400MHz,CDCl3)δ7.82–7.61(m,2H),7.46–7.37(m,1H),7.37–7.30(m,2H),7.29–7.16(m,5H),6.48(s,1H),4.55(d,J＝8.0Hz,2H).13C NMR(100MHz,CDCl3)δ167.4,138.2,134.4,131.6,128.8,128.6,127.9,127.6,127.0,44.1.HRMS-ESI:calcd for C14H14NO+([M+H+])m/z 212.1070,found212.1070.
实施例26
先称取
Figure BDA0002881008670000161
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000162
(37.8μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000163
18.6mg，产率41％。1H NMR(400MHz,CDCl3)δ7.69(d,J＝8.0Hz,2H),7.47(t,J＝8.0Hz,1H),7.39(t,J＝8.0Hz,2H),7.32(t,J＝8.0Hz,2H),7.24(t,J＝8.0Hz,3H),6.22(s,1H),3.71(q,J＝8.0Hz,2H),2.93(t,J＝8.0Hz,2H).13C NMR(100MHz,CDCl3)δ167.5,138.9,134.6,131.4,128.8,128.7,128.5,126.8,126.6,41.1,35.7.HRMS-ESI:calcd for C15H16NO+([M+H+])m/z 226.1226,found 226.1226.
实施例27
先称取
Figure BDA0002881008670000164
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000165
(30.3μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000166
22.5mg，产率64％。1H NMR(400MHz,CDCl3)δ7.75(dd,J＝4.0,4.0Hz,2H),7.47(dd,J＝8.0,4.0Hz,1H),7.45–7.32(m,2H),5.94(s,1H),4.13(ddd,J＝8.0,4.0,4.0Hz,1H),1.57(dd,J＝8.0,8.0Hz,2H),1.23(d,J＝4.0Hz,3H),0.97(t,J＝8.0Hz,3H).13C NMR(100MHz,CDCl3)δ166.9,135.1,131.2,128.5,126.8,47.1,29.8,20.5,10.4.HRMS-ESI:calcd for C11H16NO+([M+H+])m/z 178.1226,found 178.1228.
实施例28
先称取
Figure BDA0002881008670000171
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000172
(34.3μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000173
23.2mg，产率57％。1H NMR(400MHz,CDCl3)δ7.83–7.68(m,2H),7.48(ddd,J＝4.0,4.0,4.0Hz,1H),7.42(dd,J＝4.0,4.0Hz,2H),6.01(s,1H),4.13–3.84(m,1H),2.10–1.97(m,2H),1.80–1.72(m,2H),1.70–1.59(m,1H),1.42(td,J＝12.0,4.0Hz,2H),1.30–1.18(m,3H).13C NMR(100MHz,CDCl3)δ166.6,135.1,131.2,128.5,126.8,48.6,33.2,25.5,24.9.HRMS-ESI:calcd for C13H18NO+([M+H+])m/z 204.1383,found 204.1389.
实施例29
先称取
Figure BDA0002881008670000174
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000175
(29.8μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000176
24.8mg，产率70％。1H NMR(400MHz,CDCl3)δ7.86–7.69(m,2H),7.58–7.46(m,1H),7.45–7.34(m,2H),6.27(s,1H),3.37–3.20(m,2H),1.90(dt,J＝8.0,4.0Hz,1H),0.98(d,J＝8.0Hz,6H).13C NMR(100MHz,CDCl3)δ167.6,134.9,131.3,128.5,126.8,47.3,28.6,20.1.HRMS-ESI:calcd for C11H16NO+([M+H+])m/z178.1226,found 178.1225.
实施例30
先称取
Figure BDA0002881008670000181
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000182
(2MinTHF)(150.0μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000183
22.0mg，产率74％。1H NMR(400MHz,CDCl3)δ7.57–7.29(m,5H),3.05(d,J＝12.0Hz,6H).13C NMR(100MHz,CDCl3)δ171.6,136.3,129.5,128.3,127.0,39.5,35.3.HRMS-ESI:calcd for C9H12NO+([M+H+])m/z 150.0913,found 150.0915.
实施例31
先称取
Figure BDA0002881008670000184
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000185
(30.9μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000186
25.9mg，产率73％。1H NMR(400MHz,CDCl3)δ7.63–7.29(m,5H),3.75–3.43(m,2H),3.37–3.04(m,2H),1.47–1.20(m,3H),1.17–0.94(m,3H).13CNMR(100MHz,CDCl3)δ171.3,137.2,129.0,128.3,126.2,43.2,39.2,14.1,12.9.HRMS-ESI:calcd for C11H16NO+([M+H+])m/z 178.1226,found 178.1222.
实施例32
先称取
Figure BDA0002881008670000187
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000191
(38.7μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000192
20.0mg，产率44％。1H NMR(400MHz,CDCl3)δ7.69–7.43(m,2H),7.43–7.34(m,5H),7.34–7.23(m,2H),7.23–6.96(m,1H),5.07–4.21(m,2H),3.27–2.58(m,3H).13C NMR(100MHz,CDCl3)δ171.6,137.0,136.6,136.2,129.6,128.7,128.4,128.2,127.5,127.0,126.8,55.1,50.8,37.0,33.1.HRMS-ESI:calcd for C15H16NO+([M+H+])m/z 226.1226,found 226.1226.
实施例33
先称取
Figure BDA0002881008670000193
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000194
(57.6μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000195
27.1mg，产率45％。1H NMR(400MHz,CDCl3)δ7.68–7.46(m,2H),7.45–7.37(m,2H),7.37–7.32(m,4H),7.32–7.21(m.4H),7.20–6.94(m,2H),4.70(s,2H),4.40(s,2H).13C NMR(100MHz,CDCl3)δ172.2,136.2,129.6,128.7,128.5,128.4,127.6,127.0,126.7,51.5,46.9.HRMS-ESI:calcd for C21H20NO+([M+H+])m/z 302.1539,found 302.1532.
实施例34
先称取
Figure BDA0002881008670000196
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000197
(27.5μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000201
35.1mg，产率93％。1H NMR(400MHz,CDCl3)δ7.82–7.11(m,5H),3.71(s,2H),3.34(s,2H),1.68(s,4H),1.52(s,2H).13C NMR(100MHz,CDCl3)δ170.3,136.5,129.3,128.4,126.8,48.7,43.1,26.5,25.6,24.6.HRMS-ESI:calcd forC12H16NO+([M+H+])m/z 190.1226,found 190.1223.
实施例35
先称取
Figure BDA0002881008670000202
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000203
(39.8μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000204
28.8mg，产率66％。1H NMR(400MHz,CDCl3)δ7.62–7.29(m,5H),4.69(d,J＝8.0Hz,1H),3.63(d,J＝8.0Hz,1H),2.48(s,1H),2.20(s,1H),1.86(d,J＝8.0Hz,1H),1.72(s,1H),1.60(s,1H),0.96(s,3H),0.86–0.80(m,1H),0.79(s,3H).13C NMR(100MHz,CDCl3)δ170.0,136.5,129.3,128.4,126.8,54.8,49.1,42.4,32.1,31.0,19.1,18.8.HRMS-ESI:calcd for C14H20NO+([M+H+])m/z 218.1539,found 218.1535.
实施例36
先称取
Figure BDA0002881008670000205
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000206
(38.3μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000211
25.9mg，产率57％。1H NMR(400MHz,CDCl3)δ7.77(d,J＝8.0Hz,2H),7.57–7.04(m,8H),6.40(s,1H),5.47–5.16(m,1H),1.60(d,J＝8.0Hz,3H).13C NMR(100MHz,CDCl3)δ166.6,143.1,134.6,131.4,128.7,128.5,127.4,126.9,126.2,49.2,21.7.HRMS-ESI:calcd for C15H16NO+([M+H+])m/z 226.1226,found 226.1220.
实施例37
先称取
Figure BDA0002881008670000212
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000213
(40.9μL,0.3mmol)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000214
21.4mg，产率45％。1H NMR(400MHz,CDCl3)δ7.94–7.69(m,2H),7.50(d,J＝8.0Hz,1H),7.44(t,J＝8.0Hz,2H),6.69(s,1H),4.14(d,J＝4.0Hz,2H),1.51(s,9H).13C NMR(100MHz,CDCl3)δ169.2,167.2,133.9,131.70,128.5,127.0,82.5,42.5,28.0.HRMS-ESI:calcd for C13H17NNaO3 +([M+Na+])m/z 258.1101,found258.1103.
实施例38
先称取
Figure BDA0002881008670000215
(24.4mg,0.2mmol)，
Figure BDA0002881008670000216
(46.1mg,0.3mmol)，NaHCO3(25.2mg,0.3mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000217
24.8mg，产率56％。1H NMR(400MHz,CDCl3)δ7.91–7.68(m,2H),7.50–7.40(m,1H),7.40–7.30(m,2H),7.07(d,J＝8.0Hz,1H),4.47(p,J＝8.0Hz,1H),4.19(q,J＝8.0Hz,2H),1.47(d,J＝4.0Hz,3H),1.26(t,J＝8.0Hz,3H).13C NMR(100MHz,CDCl3)δ173.2,166.9,133.9,131.6,128.4,127.0,61.5,48.5,18.3,14.1.HRMS-ESI:calcd for C12H16NO3 +([M+H+])m/z 222.1125,found 222.1125.
实施例39
先称取
Figure BDA0002881008670000221
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000222
(19.2μL,0.3mmol)和
Figure BDA0002881008670000223
(26.3μL,0.2mmol)然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000224
16.6mg，产率52％。1H NMR(400MHz,CDCl3)δ7.89–7.74(m,2H),7.59–7.50(m,1H),7.49–7.40(m,2H),6.49(s,1H),4.27(dd,J＝4.0,4.0Hz,2H),2.48–2.18(m,1H).13C NMR(100MHz,CDCl3)δ167.2,133.8,131.9,128.75127.1,79.5,72.0,29.9.HRMS-ESI:calcd for C10H10NO+([M+H+])m/z160.0757,found 160.0760.
实施例40
先称取
Figure BDA0002881008670000225
(24.4mg,0.2mmol)，H3C-NH2 HCl(67.5mg,0.3mmol)，NaHCO3(25.2mg,0.3mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000226
19.2mg，产率71％。1H NMR(400MHz,CDCl3)δ7.85–7.70(m,2H),7.54–7.46(m,1H),7.46–7.37(m,2H),6.26(s,1H),3.02(d,J＝4.0Hz,3H).13C NMR(100MHz,CDCl3)δ168.3,134.6,131.3,128.5,126.8,26.8.HRMS-ESI:calcd for C8H10NO+([M+H+])m/z 136.0757,found 136.0764.
实施例41
先称取
Figure BDA0002881008670000231
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入质量分数25％的氨水(22.4μL,0.3mmol)和
Figure BDA0002881008670000232
(29.9μL,0.2mmol)然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000233
6.1mg，产率25％。1H NMR(400MHz,CDCl3)δ7.92–7.72(m,2H),7.60–7.50(m,1H),7.49–7.36(m,2H),6.26(s,2H).13C NMR(100MHz,CDCl3)δ169.8,133.4,132.1,128.7,127.4.HRMS-ESI:calcd forC7H8NO+([M+H+])m/z 122.0600,found 122.0604.
实施例42
先称取
Figure BDA0002881008670000234
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000235
(27.4μL,0.3mmol)和
Figure BDA0002881008670000236
(26.3μL,0.2mmol)然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000237
24.6mg，产率62％。1H NMR(400MHz,CDCl3)δ7.95(s,1H),7.89–7.78(m,2H),7.64(d,J＝8.0Hz,2H),7.58–7.50(m,1H),7.50–7.41(m,2H),7.36(t,J＝8.0Hz,2H),7.22–7.07(m,1H).13C NMR(100MHz,CDCl3)δ165.8,137.9,135.0,131.8,129.1,128.8,127.0,124.6,120.2.HRMS-ESI:calcd forC13H12NO+([M+H+])m/z 198.0913,found 198.0914.
实施例43
先称取
Figure BDA0002881008670000238
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol),
Figure BDA0002881008670000241
(51.6mg,0.3mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000242
(26.3μL,0.2mmol)然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000243
34.8mg，产率63％。1HNMR(400MHz,DMSO-d6)δ10.38(s,1H),8.06–7.88(m,2H),7.81–7.72(m,2H),7.66–7.57(m,1H),7.57–7.41(m,4H).13C NMR(100MHz,DMSO-d6)δ166.1,139.0,135.1,132.2,131.9,128.9,128.1,122.7,115.8.HRMS-ESI:calcd for C13H10 78.9183BrNNaO+([M+Na+])m/z297.9838,found 297.9844.
实施例44
先称取
Figure BDA0002881008670000244
(24.4mg,0.2mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(2.3mg,0.002mmol)，PPh3(52.5mg,0.2mmol),
Figure BDA0002881008670000245
(32.1mg,0.3mmol)和Co(dmgH)(dmgH2)Cl2(3.6mg,0.01mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(6.0mL)，再慢慢加入
Figure BDA0002881008670000246
(26.3μL,0.2mmol)然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000247
23.3mg，产率52％。1H NMR(400MHz,CDCl3)δ7.88(s,1H),7.86–7.80(m,2H),7.60–7.49(m,3H),7.49–7.39(m,2H),7.16(d,J＝8.0Hz,2H),2.33(s,3H).13C NMR(100MHz,CDCl3)δ164.6,134.3,134.0,133.2,130.6,128.5,127.7,125.9,119.3,19.8.HRMS-ESI:calcd for C14H14NO+([M+H+])m/z212.1070,found 212.1078.
实施例45
先称取
Figure BDA0002881008670000248
(145.7mg,0.8mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(9.3mg,0.008mmol)，PPh3(209.8mg,0.8mmol)，
Figure BDA0002881008670000251
(147.8mg,1.2mmol)，和Co(dmgH)(dmgH2)Cl2(16.1mg,0.04mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(24.0mL)，然后置于蓝色LEDs灯照射下，室温反应12h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000252
151.5mg，产率66％。1H NMR(400MHz,CDCl3)δ7.68–7.37(m,2H),7.30(dd,J＝4.0,4.0Hz,1H),7.11(d,J＝8.0Hz,2H),6.79(t,J＝8.0Hz,3H),6.70(t,J＝8.0Hz,1H),4.49(d,J＝8.0Hz,2H),3.84(d,J＝16.0Hz,6H).13C NMR(100MHz,CDCl3)δ167.5,155.9,151.8,148.9,129.4,129.2,126.6,119.6,115.7,110.5,110.3,55.9,55.9,43.8.HRMS-ESI:calcd for C16H18NO4 +([M+H+])m/z 288.1230,found288.1238.
实施例46
先称取
Figure BDA0002881008670000253
(357.4mg,1.0mmol)，
Figure BDA0002881008670000254
(323.5mg,1.5mmol)，NaHCO3(126.0mg,1.5mmol)，[Ir(dF(CF3)ppy)2(dtbbpy)]PF6(11.7mg,0.01mmol)，PPh3(262.3mg,1.0mmol)和Co(dmgH)(dmgH2)Cl2(18.1mg,0.05mmol)加入到反应管中，加塞密封，通过真空管线抽换气三次，在氮气氛围下，加入二氯甲烷(30.0mL)，然后置于蓝色LEDs灯照射下，室温反应18h，搅拌速度为1200r/min。TLC监测反应结束后，旋蒸除去溶剂，柱层析(300-400目层析硅胶，洗脱剂：石油醚-乙酸乙酯)分离得到产物
Figure BDA0002881008670000255
242.7mg，产率47％。1H NMR(400MHz,CDCl3)δ7.48–7.31(m,10H),7.31–7.21(m,3H),7.20–7.10(m,2H),6.95(d,J＝8.0Hz,1H),5.92(d,J＝8.0Hz,1H),5.25–5.01(m,4H),4.92–4.75(m,1H),4.70–4.49(m,1H),3.71(s,3H),3.25–2.91(m,3H),2.75(dd,J＝8.0,4.0Hz,1H).13C NMR(100MHz,CDCl3)δ171.6,171.3,169.9,155.9,135.9,135.6,135.3,129.2,128.5,128.39,128.3,128.2,128.1,127.1,67.3,66.9,53.4,52.3,50.8,37.7,36.0.HRMS-ESI:calcd for C29H31N2O7 +([M+H+])m/z 519.2126,found 519.2127.

Claims (6)

1.一种从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述方法为：以R取代的羧酸和R1'、R2'取代的胺类为原料，三苯基膦为脱氧剂，在二氯甲烷中，惰性气氛下，并在蓝光照射下，以[Ir(dF(CF3)ppy)2(dtbbpy)]PF6为光催化剂，Co(dmgH)(dmgH2)Cl2为金属配合物催化剂，反应得到酰胺类化合物；
所述R为C1-C6的直链烷基、C1-C6的环状烷基、苯基、萘基、被保护的氨基、呋喃基、吡啶基、取代的苯基、取代的被保护的氨基；
所述R1'为氢基、C1-C6的直链烷基、C1-C6的环状烷基、苄基、羧基、酯基、取代的苄基、取代的羧基、取代的酯基、苯基或取代的苯基；
所述R2'为氢基、C1-C6的直链烷基、C1-C6的环状烷基、苄基、羧基、酯基、取代的苄基、取代的羧基、取代的酯基、苯基或取代的苯基。
2.根据权利要求1所述从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述羧酸与胺类的物质的量比为1：1.5-2.0。
3.根据权利要求2所述从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述羧酸与三苯基膦的物质的量比为1：1.0-1.5。
4.根据权利要求3所述从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述光催化剂的用量为羧酸物质的量的1-3％。
5.根据权利要求4所述从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述金属配合物催化剂的用量为羧酸物质的量的5-10％。
6.根据权利要求5所述从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法，其特征在于：所述反应的条件为：室温反应3-18h，搅拌速度为1200-1500r/min。
CN202011635404.XA 2020-12-31 2020-12-31 从羧酸以铱、钴配合物为催化剂并在蓝光照射下制备酰胺的方法 Active CN112778238B (zh)

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