高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (9): 2798.doi: 10.7503/cjcu20210260
收稿日期:
2021-04-19
出版日期:
2021-09-10
发布日期:
2021-09-08
通讯作者:
刘晟
E-mail:lsheng@126.com
基金资助:
GUO Yang1,2, LIN Kai2, XIE Kaiqiang2, LIU Sheng1,2()
Received:
2021-04-19
Online:
2021-09-10
Published:
2021-09-08
Contact:
LIU Sheng
E-mail:lsheng@126.com
Supported by:
摘要:
发展了一种合成靛红的新方法, 并进行了底物扩展, 得到了一系列靛红类化合物. 以N-烷基取代的丙烯酰苯胺类化合物为原料, 在醋酸钯、 碘化亚铜和氧气的催化及参与下, 以42%~87%的产率合成了N-烷基化的靛红衍生物. 利用该方法制备了23个靛红类化合物, 并提出了可能的反应机理. 该合成路线减少了保护基的使用, 简洁高效.
中图分类号:
TrendMD:
郭阳, 林凯, 谢凯强, 刘晟. 基于钯铜催化合成靛红类化合物的新方法. 高等学校化学学报, 2021, 42(9): 2798.
GUO Yang, LIN Kai, XIE Kaiqiang, LIU Sheng. Novel Approach to Isatins via Pd-Cu Catalyzed Oxidative Transformation. Chem. J. Chinese Universities, 2021, 42(9): 2798.
Compd. | Yield(%) | m. p./℃ | HRMS(calcd.), m/z[M+H]+ |
---|---|---|---|
3a | 83 | 132—133 | 162.0553(162.0550) |
3b | 85 | 93—94 | 176.0715(176.0706) |
3c | 75 | 34—35 | 204.1028(204.019) |
3d | 70 | 68—69 | 190.0869(190.0863) |
3e | 74 | 121—122 | 238.0865(238.0863) |
3f | 87 | 170—171 | 268.0977(268.0968) |
3g | 51 | 178—179 | 363.9835(363.9829) |
3k | 76 | 135—136 | 176.0711(176.0706) |
3l | 77 | 139—140 | 282.1133(282.1125) |
3m | 68 | 194—195 | 252.1023(252.1019) |
3n | 53 | 145—146 | 296.1288(296.1281) |
3o | 58 | 166—167 | 324.1596(324.1594) |
3p | 62 | 158—159 | 310.1444(310.1438) |
3q | 10 | 119—120 | 252.1027(252.1019) |
3q' | 65 | 119—120 | 252.1023(252.1019) |
3r | 77 | 147—148 | 298.1080(298.1074) |
3s | 57 | 69—70 | 306.0746(306.0736) |
3t | 56 | 126—127 | 210.0324(210.0316) |
3u | 45 | 126—127 | 210.0322(210.0316) |
3v | 60 | 120—121 | 180.0463(180.0455) |
3w | 45 | 152—153 | 220.0612(220.0604) |
3x | 42 | 182—183 | 188.0723(188.0706) |
3y | 56 | 195—196 | 238.0506(238.0499) |
Table 1 Yields, melting points and HRMS data of compounds 3a—3g and 3k—3y
Compd. | Yield(%) | m. p./℃ | HRMS(calcd.), m/z[M+H]+ |
---|---|---|---|
3a | 83 | 132—133 | 162.0553(162.0550) |
3b | 85 | 93—94 | 176.0715(176.0706) |
3c | 75 | 34—35 | 204.1028(204.019) |
3d | 70 | 68—69 | 190.0869(190.0863) |
3e | 74 | 121—122 | 238.0865(238.0863) |
3f | 87 | 170—171 | 268.0977(268.0968) |
3g | 51 | 178—179 | 363.9835(363.9829) |
3k | 76 | 135—136 | 176.0711(176.0706) |
3l | 77 | 139—140 | 282.1133(282.1125) |
3m | 68 | 194—195 | 252.1023(252.1019) |
3n | 53 | 145—146 | 296.1288(296.1281) |
3o | 58 | 166—167 | 324.1596(324.1594) |
3p | 62 | 158—159 | 310.1444(310.1438) |
3q | 10 | 119—120 | 252.1027(252.1019) |
3q' | 65 | 119—120 | 252.1023(252.1019) |
3r | 77 | 147—148 | 298.1080(298.1074) |
3s | 57 | 69—70 | 306.0746(306.0736) |
3t | 56 | 126—127 | 210.0324(210.0316) |
3u | 45 | 126—127 | 210.0322(210.0316) |
3v | 60 | 120—121 | 180.0463(180.0455) |
3w | 45 | 152—153 | 220.0612(220.0604) |
3x | 42 | 182—183 | 188.0723(188.0706) |
3y | 56 | 195—196 | 238.0506(238.0499) |
Compd. | 1H NMR(600 MHz, CDCl3), δ | 13C NMR(150 MHz, CDCl3), δ |
---|---|---|
3a | 7.64—7.57(m, 2H), 7.13(t, J=7.5 Hz, 1H), 6.90(d, J=7.9 Hz, 1H), 3.25 (s, 3H) | 183.3, 158.2, 151.4, 138.4, 125.2, 123.8, 117.4, 109.9, 26.2 |
3b | 7.63—7.54(m, 2H), 7.13—7.07(m, 1H), 6.91(d, J=8.2 Hz, 1H), 3.81—3.76(q, J=6.0 Hz, 2H) , 1.31(t, J=7.3 Hz, 3H) | 183.7, 157.8, 150.6, 138.3, 125.4, 123.6, 117.6, 110.0, 34.9, 12.5 |
3c | 7.64—7.52(m, 2H), 7.10(t, J=7.5 Hz, 1H), 6.90(d, J=8.1 Hz, 1H), 3.72(t, J=7.3 Hz, 2H), 1.68(q, J=7.5 Hz, 2H), 1.41(q, J=7.5 Hz, 2H), 0.96(t, J=7.4 Hz, 3H) | 183.6, 158.1, 151.0, 138.3, 125.4, 123.5, 117.5, 110.1, 39.2, 28.7, 19.4, 13.6 |
3d | 7.60—7.53(m, 2H), 7.08(t, J=7.4 Hz, 1H), 7.03(d, J=8.0 Hz, 1H), 4.52(td, J=7.1, 14.0 Hz, 1H), 1.51(s, 3H), 1.50(s, 3H) | 183.8, 157.8, 150.4, 138.1, 125.5, 123.2, 117.8, 111.3, 44.7, 19.3 |
3e | 7.62(d, J=7.4 Hz, 1H), 7.49(d, J=7.8 H, 1H), 7.37—7.28(m, 5H), 7.10(t, J=7.4 Hz, 1H), 6.79(d, J=7.7 Hz, 1H), 4.94(s, 2H) | 183.2, 158.2, 150.7, 138.3, 134.4, 129.0, 128.1, 127.4, 125.4, 123.8, 117.6, 111.0, 44.0 |
3f | 7.59(d, J=6.8 Hz, 1H), 7.51—7.46(m, 1H), 7.27(d, J=8.8 Hz, 2H), 7.10—7.06(m, 1H), 6.87(d, J=8.8 Hz, 2H), 6.81(d, J=8.0 Hz, 1H), 4.86(s, 2H), 3.78(s, 3H) | 183.3, 159.4, 158.7, 150.3, 138.0, 128.9, 127.3, 124.5, 123.73, 117.7, 114.1, 111.2, 55.1, 42.4 |
3g | 7.90(d, J=7.8 Hz, 1H), 7.66(d, J=7.4 Hz, 1H), 7.51(td, J=7.8, 1.1 Hz, 1H), 7.29 (t, J=7.5 Hz, 1H) , 7.10—7.16(m, 2H), 7.02(t, J=7.3 Hz, 1H), 6.68 (d, J=8.0 Hz, 1H), 4.98(s, 2H) | 182.9, 158.3, 150.4, 139.9, 138.5, 135.9, 129.7, 128.8, 127.1, 125.5, 124.1, 117.7, 111.3, 97.6, 49.1 |
3k | 7.43—7.36(m, 2H), 6.79(d, J=8.2 Hz, 1H), 3.23(s, 3H), 2.33(s, 3H) | 183.6, 158.3, 149.2, 138.7, 133.6, 125.6, 117.4, 109.7, 26.2, 20.6 |
3l | 7.42(s, 1H), 7.31—7.28(m, 2H), 7.27(s, 1H), 6.89—6.87(m, 2H), 6.70(d, J=8.0 Hz, 1H), 4.86(s, 2H), 3.80(s, 3H), 2.31(s, 3H) | 183.6, 159.3, 158.2, 148.5, 138.6, 133.6, 128.8, 126.5, 125.6, 117.6, 114.3, 110.8, 55.2, 43.4, 20.8 |
3m | 7.50(d, J=7.6 Hz, 1H), 7.37(d, J=0.7 Hz, 1H), 7.35(d, J=3.5 Hz, 2H), 7.34(s, 1H) , 7.32 (s, 1H) , 6.90(d, J=7.6 Hz, 1H), 6.60(s, 1H), 4.92(s, 2H), 2.36(s, 3H) | 183.6, 159.6, 148.6, 142.5, 136.2, 129.1, 127.7, 125.6, 124.1, 123.6, 122.0, 118.8, 45.3, 18.6 |
Compd. | 1H NMR(600 MHz, CDCl3), δ | 13C NMR(150 MHz, CDCl3), δ |
3n | 7.54(dd, J=1.2, 7.4 Hz, 1H), 7.34(d, J=7.8 Hz, 1H), 7.13(d, J=8.7 Hz, 2H), 7.07(t, J=7.5 Hz, 1H), 6.87(d, J=8.7 Hz, 2H), 5.11(s, 2H), 3.78(s, 3H), 2.61(q, J=7.6 Hz, 2H), 1.11(t, J=7.5 Hz, 3H) | 183.6, 159.8, 159.1, 147.8, 141.0, 130.6, 128.6, 127.9, 126.9, 124.2, 123.6, 119.1, 114.4, 55.3, 45.1, 24.3, 16.0 |
3o | 7.65(d, J=1.8 Hz, 1H), 7.52(dd, J=1.8, 8.5 Hz, 1H), 7.29(s, 1H), 7.27(s, 1H), 6.87(d, J=8.5 Hz, 2H), 6.74(d, J=8.5 Hz, 1H), 4.85(s, 2H), 3.79(s, 3H), 1.27(s, 9H) | 183.8, 159.4, 158.5, 148.5, 147.2, 135.3, 128.9, 126.7, 122.4, 117.5, 114.3, 110.6, 55.2, 43.5, 34.5, 31.1 |
3p | 7.52(d, J=7.7 Hz, 1H), 7.28(d, J=8.7 Hz, 2H), 6.93(d, J=7.8 Hz, 1H), 6.88(d, J=8.4 Hz, 2H), 6.65(s, 1H), 4.86(s, 2H), 3.79(s, 3H), 2.94—2.81(m, 1H), 1.20(d, J=6.8 Hz, 6H) | 182.7, 161.3, 159.4, 158.9, 151.2, 128.9,126.7, 125.5, 121.9, 115.8, 114.3, 109.2, 55.3, 43.4, 35.2, 23.3 |
3q | 7.36—7.34(m, 1H), 7.34(d, J=2.0 Hz, 3H), 7.32—7.30(m, 2H), 6.86(d, J=7.8 Hz, 1H), 6.59(d, J=7.8 Hz, 1H), 4.92(s, 2H), 2.58(s, 3H) | 183.7, 158.2, 150.7, 141.3, 137.4, 134.7, 129.0, 128.0, 127.3, 126.1, 115.8, 108.2, 43.9, 18.1 |
3q' | 7.50(d, J=7.6 Hz, 1H), 7.39—7.37(m, 1H), 7.36(d, J=3.3 Hz, 2H), 7.35—7.29(m, 2H), 6.90(d, J=7.6 Hz, 1H), 6.60(s, 1H), 4.92(s, 2H), 2.36(s, 3H) | 182.4, 158.9, 151.1, 150.7, 134.6, 128.9, 128.0, 127.2, 125.3, 124.5, 115.5, 111.5, 43.8, 22.9 |
3r | 7.28(d, J=9.3 Hz, 2H), 7.16(d, J=2.7 Hz, 1H), 7.05(dd, J=2.7, 8.5 Hz, 1H), 6.92—6.85(m, 2H), 6.72(d, J=8.7 Hz, 1H), 4.86(s, 2 H), 3.80(s, 3H), 3.79(s, 3H) | 183.6, 159.3, 158.3, 148.5, 138.6, 133.6, 128.8, 126.5, 125.6, 117.6, 114.3, 110.8, 55.2, 43.4, 20.6 |
3s | 7.87(s, 1H), 7.76(dd, J=1.3, 8.4 Hz, 1H), 7.39—7.36(m, 2H), 7.36—7.31 (m, 3H), 6.91(d, J=8.4 Hz, 1H), 4.99(s, 2H) | 182.0, 157.8, 153.0, 135.2, 135.1, 133.8, 129.3, 128.5, 127.4, 122.6, 117.5, 111.3, 44.4 |
3t | 7.58—7.54(m, 2H), 6.89—6.87(m, 1H), 3.79(q, J=7.3 Hz, 2H), 1.31 (t, J=7.3 Hz, 3H) | 182.6, 157.3, 148.9, 137.6, 129.4, 125.4, 118.4, 111.2, 35.1, 12.4 |
3u | 7.58—7.51(m, 2H), 7.07(t, J=7.7 Hz, 1H), 4.20(q, J=7.1 Hz, 2H), 1.38(t, J=7.2 Hz, 3H) | 182.8, 158.3, 146.3, 140.5, 124.6, 124.1, 120.5, 117.1, 37.0, 14.7 |
3v | 7.35—7.32(m, 2H), 6.88—6.86(m, 1H), 3.27(s, 3H) | 182.7, 160.2, 158.6, 158.0, 147.5, 124.7, 112.5, 111.0, 26.3 |
3w | 8.33(d, J=8.1 Hz, 1H), 8.26(s, 1H), 6.98(d, J=8.1 Hz, 1H), 3.93(s, 1H), 3.31(s, 1H) | 182.2, 165.4, 158.2, 154.5, 140.0, 126.6, 126.0, 117.1, 109.7, 52.5, 26.5 |
3x | 7.40(d, J=7.2 Hz, 1H), 7.34(d, J=7. 9 Hz, 1H), 7.00(t, J=7.5 Hz, 1H), 3.85—3.59(m, 2H), 2.79(t, J=6.1 Hz, 2H), 2.18—1.95(m, 2H) | 184.0, 156.9, 147.6, 137.1, 123.2, 123.0, 121.9, 115.8, 38.4, 23.9, 20.2 |
3y | 7.60(d, J=7.6 Hz, 1H), 7.20(d, J=8.5 Hz, 1H), 7.16—7.12(m, 3H), 6.71—6.51(m, 2H) | 186.4, 149.7, 148.8, 143.9, 135.2, 134.8, 133.4, 132.9, 130.5, 125.5, 116.2, 106.9 |
Table 2 1H NMR and 13C NMR data of compounds 3a—3g and 3k—3y
Compd. | 1H NMR(600 MHz, CDCl3), δ | 13C NMR(150 MHz, CDCl3), δ |
---|---|---|
3a | 7.64—7.57(m, 2H), 7.13(t, J=7.5 Hz, 1H), 6.90(d, J=7.9 Hz, 1H), 3.25 (s, 3H) | 183.3, 158.2, 151.4, 138.4, 125.2, 123.8, 117.4, 109.9, 26.2 |
3b | 7.63—7.54(m, 2H), 7.13—7.07(m, 1H), 6.91(d, J=8.2 Hz, 1H), 3.81—3.76(q, J=6.0 Hz, 2H) , 1.31(t, J=7.3 Hz, 3H) | 183.7, 157.8, 150.6, 138.3, 125.4, 123.6, 117.6, 110.0, 34.9, 12.5 |
3c | 7.64—7.52(m, 2H), 7.10(t, J=7.5 Hz, 1H), 6.90(d, J=8.1 Hz, 1H), 3.72(t, J=7.3 Hz, 2H), 1.68(q, J=7.5 Hz, 2H), 1.41(q, J=7.5 Hz, 2H), 0.96(t, J=7.4 Hz, 3H) | 183.6, 158.1, 151.0, 138.3, 125.4, 123.5, 117.5, 110.1, 39.2, 28.7, 19.4, 13.6 |
3d | 7.60—7.53(m, 2H), 7.08(t, J=7.4 Hz, 1H), 7.03(d, J=8.0 Hz, 1H), 4.52(td, J=7.1, 14.0 Hz, 1H), 1.51(s, 3H), 1.50(s, 3H) | 183.8, 157.8, 150.4, 138.1, 125.5, 123.2, 117.8, 111.3, 44.7, 19.3 |
3e | 7.62(d, J=7.4 Hz, 1H), 7.49(d, J=7.8 H, 1H), 7.37—7.28(m, 5H), 7.10(t, J=7.4 Hz, 1H), 6.79(d, J=7.7 Hz, 1H), 4.94(s, 2H) | 183.2, 158.2, 150.7, 138.3, 134.4, 129.0, 128.1, 127.4, 125.4, 123.8, 117.6, 111.0, 44.0 |
3f | 7.59(d, J=6.8 Hz, 1H), 7.51—7.46(m, 1H), 7.27(d, J=8.8 Hz, 2H), 7.10—7.06(m, 1H), 6.87(d, J=8.8 Hz, 2H), 6.81(d, J=8.0 Hz, 1H), 4.86(s, 2H), 3.78(s, 3H) | 183.3, 159.4, 158.7, 150.3, 138.0, 128.9, 127.3, 124.5, 123.73, 117.7, 114.1, 111.2, 55.1, 42.4 |
3g | 7.90(d, J=7.8 Hz, 1H), 7.66(d, J=7.4 Hz, 1H), 7.51(td, J=7.8, 1.1 Hz, 1H), 7.29 (t, J=7.5 Hz, 1H) , 7.10—7.16(m, 2H), 7.02(t, J=7.3 Hz, 1H), 6.68 (d, J=8.0 Hz, 1H), 4.98(s, 2H) | 182.9, 158.3, 150.4, 139.9, 138.5, 135.9, 129.7, 128.8, 127.1, 125.5, 124.1, 117.7, 111.3, 97.6, 49.1 |
3k | 7.43—7.36(m, 2H), 6.79(d, J=8.2 Hz, 1H), 3.23(s, 3H), 2.33(s, 3H) | 183.6, 158.3, 149.2, 138.7, 133.6, 125.6, 117.4, 109.7, 26.2, 20.6 |
3l | 7.42(s, 1H), 7.31—7.28(m, 2H), 7.27(s, 1H), 6.89—6.87(m, 2H), 6.70(d, J=8.0 Hz, 1H), 4.86(s, 2H), 3.80(s, 3H), 2.31(s, 3H) | 183.6, 159.3, 158.2, 148.5, 138.6, 133.6, 128.8, 126.5, 125.6, 117.6, 114.3, 110.8, 55.2, 43.4, 20.8 |
3m | 7.50(d, J=7.6 Hz, 1H), 7.37(d, J=0.7 Hz, 1H), 7.35(d, J=3.5 Hz, 2H), 7.34(s, 1H) , 7.32 (s, 1H) , 6.90(d, J=7.6 Hz, 1H), 6.60(s, 1H), 4.92(s, 2H), 2.36(s, 3H) | 183.6, 159.6, 148.6, 142.5, 136.2, 129.1, 127.7, 125.6, 124.1, 123.6, 122.0, 118.8, 45.3, 18.6 |
Compd. | 1H NMR(600 MHz, CDCl3), δ | 13C NMR(150 MHz, CDCl3), δ |
3n | 7.54(dd, J=1.2, 7.4 Hz, 1H), 7.34(d, J=7.8 Hz, 1H), 7.13(d, J=8.7 Hz, 2H), 7.07(t, J=7.5 Hz, 1H), 6.87(d, J=8.7 Hz, 2H), 5.11(s, 2H), 3.78(s, 3H), 2.61(q, J=7.6 Hz, 2H), 1.11(t, J=7.5 Hz, 3H) | 183.6, 159.8, 159.1, 147.8, 141.0, 130.6, 128.6, 127.9, 126.9, 124.2, 123.6, 119.1, 114.4, 55.3, 45.1, 24.3, 16.0 |
3o | 7.65(d, J=1.8 Hz, 1H), 7.52(dd, J=1.8, 8.5 Hz, 1H), 7.29(s, 1H), 7.27(s, 1H), 6.87(d, J=8.5 Hz, 2H), 6.74(d, J=8.5 Hz, 1H), 4.85(s, 2H), 3.79(s, 3H), 1.27(s, 9H) | 183.8, 159.4, 158.5, 148.5, 147.2, 135.3, 128.9, 126.7, 122.4, 117.5, 114.3, 110.6, 55.2, 43.5, 34.5, 31.1 |
3p | 7.52(d, J=7.7 Hz, 1H), 7.28(d, J=8.7 Hz, 2H), 6.93(d, J=7.8 Hz, 1H), 6.88(d, J=8.4 Hz, 2H), 6.65(s, 1H), 4.86(s, 2H), 3.79(s, 3H), 2.94—2.81(m, 1H), 1.20(d, J=6.8 Hz, 6H) | 182.7, 161.3, 159.4, 158.9, 151.2, 128.9,126.7, 125.5, 121.9, 115.8, 114.3, 109.2, 55.3, 43.4, 35.2, 23.3 |
3q | 7.36—7.34(m, 1H), 7.34(d, J=2.0 Hz, 3H), 7.32—7.30(m, 2H), 6.86(d, J=7.8 Hz, 1H), 6.59(d, J=7.8 Hz, 1H), 4.92(s, 2H), 2.58(s, 3H) | 183.7, 158.2, 150.7, 141.3, 137.4, 134.7, 129.0, 128.0, 127.3, 126.1, 115.8, 108.2, 43.9, 18.1 |
3q' | 7.50(d, J=7.6 Hz, 1H), 7.39—7.37(m, 1H), 7.36(d, J=3.3 Hz, 2H), 7.35—7.29(m, 2H), 6.90(d, J=7.6 Hz, 1H), 6.60(s, 1H), 4.92(s, 2H), 2.36(s, 3H) | 182.4, 158.9, 151.1, 150.7, 134.6, 128.9, 128.0, 127.2, 125.3, 124.5, 115.5, 111.5, 43.8, 22.9 |
3r | 7.28(d, J=9.3 Hz, 2H), 7.16(d, J=2.7 Hz, 1H), 7.05(dd, J=2.7, 8.5 Hz, 1H), 6.92—6.85(m, 2H), 6.72(d, J=8.7 Hz, 1H), 4.86(s, 2 H), 3.80(s, 3H), 3.79(s, 3H) | 183.6, 159.3, 158.3, 148.5, 138.6, 133.6, 128.8, 126.5, 125.6, 117.6, 114.3, 110.8, 55.2, 43.4, 20.6 |
3s | 7.87(s, 1H), 7.76(dd, J=1.3, 8.4 Hz, 1H), 7.39—7.36(m, 2H), 7.36—7.31 (m, 3H), 6.91(d, J=8.4 Hz, 1H), 4.99(s, 2H) | 182.0, 157.8, 153.0, 135.2, 135.1, 133.8, 129.3, 128.5, 127.4, 122.6, 117.5, 111.3, 44.4 |
3t | 7.58—7.54(m, 2H), 6.89—6.87(m, 1H), 3.79(q, J=7.3 Hz, 2H), 1.31 (t, J=7.3 Hz, 3H) | 182.6, 157.3, 148.9, 137.6, 129.4, 125.4, 118.4, 111.2, 35.1, 12.4 |
3u | 7.58—7.51(m, 2H), 7.07(t, J=7.7 Hz, 1H), 4.20(q, J=7.1 Hz, 2H), 1.38(t, J=7.2 Hz, 3H) | 182.8, 158.3, 146.3, 140.5, 124.6, 124.1, 120.5, 117.1, 37.0, 14.7 |
3v | 7.35—7.32(m, 2H), 6.88—6.86(m, 1H), 3.27(s, 3H) | 182.7, 160.2, 158.6, 158.0, 147.5, 124.7, 112.5, 111.0, 26.3 |
3w | 8.33(d, J=8.1 Hz, 1H), 8.26(s, 1H), 6.98(d, J=8.1 Hz, 1H), 3.93(s, 1H), 3.31(s, 1H) | 182.2, 165.4, 158.2, 154.5, 140.0, 126.6, 126.0, 117.1, 109.7, 52.5, 26.5 |
3x | 7.40(d, J=7.2 Hz, 1H), 7.34(d, J=7. 9 Hz, 1H), 7.00(t, J=7.5 Hz, 1H), 3.85—3.59(m, 2H), 2.79(t, J=6.1 Hz, 2H), 2.18—1.95(m, 2H) | 184.0, 156.9, 147.6, 137.1, 123.2, 123.0, 121.9, 115.8, 38.4, 23.9, 20.2 |
3y | 7.60(d, J=7.6 Hz, 1H), 7.20(d, J=8.5 Hz, 1H), 7.16—7.12(m, 3H), 6.71—6.51(m, 2H) | 186.4, 149.7, 148.8, 143.9, 135.2, 134.8, 133.4, 132.9, 130.5, 125.5, 116.2, 106.9 |
Entry | Solvent | Cat. | Temperature/℃ | Time/h | Yieldb(%) |
---|---|---|---|---|---|
1 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuCl | 120 | 24 | 42 |
2 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuCl2 | 120 | 24 | 10 |
3 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuBr | 120 | 18 | 38 |
4 | DMF | 0.1 mmol Pd(OAc)2, 0.1 mmol CuBr2 | 120 | 18 | 5 |
5 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 83 |
6 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol Cu2O | 120 | 18 | 25 |
7 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol Cu(OAc)2 | 120 | 18 | 0 |
8 | DMF | 0.05 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 44 |
9 | DMF | 0.1 mmol PdCl2, 2.0 mmol CuI | 120 | 24 | 20 |
10c | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 66 |
11d | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 0 |
12 | DMF | 0.1 mmol Pd(OAc)2, 0.18 mmol CuI | 120 | 24 | 63 |
13 | DMF | 0.1 mmol Pd(OAc)2, 2.2 mmol CuI | 120 | 12 | 74 |
14 | DMA | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 45 |
15 | DMSO | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 8 |
16 | Toluene | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
17 | MeCN | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
18 | Dioxane | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
19 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 110 | 24 | 64 |
20 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 130 | 12 | 72 |
Table 3 Optimization of the reaction conditionsa
Entry | Solvent | Cat. | Temperature/℃ | Time/h | Yieldb(%) |
---|---|---|---|---|---|
1 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuCl | 120 | 24 | 42 |
2 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuCl2 | 120 | 24 | 10 |
3 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuBr | 120 | 18 | 38 |
4 | DMF | 0.1 mmol Pd(OAc)2, 0.1 mmol CuBr2 | 120 | 18 | 5 |
5 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 83 |
6 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol Cu2O | 120 | 18 | 25 |
7 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol Cu(OAc)2 | 120 | 18 | 0 |
8 | DMF | 0.05 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 44 |
9 | DMF | 0.1 mmol PdCl2, 2.0 mmol CuI | 120 | 24 | 20 |
10c | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 66 |
11d | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 0 |
12 | DMF | 0.1 mmol Pd(OAc)2, 0.18 mmol CuI | 120 | 24 | 63 |
13 | DMF | 0.1 mmol Pd(OAc)2, 2.2 mmol CuI | 120 | 12 | 74 |
14 | DMA | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 45 |
15 | DMSO | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 24 | 8 |
16 | Toluene | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
17 | MeCN | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
18 | Dioxane | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 120 | 18 | 0 |
19 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 110 | 24 | 64 |
20 | DMF | 0.1 mmol Pd(OAc)2, 2.0 mmol CuI | 130 | 12 | 72 |
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