无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应

doi:10.7503/cjcu20150716

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (2): 254.doi: 10.7503/cjcu20150716

无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应

王亮^1,²(), 瞿星¹, 李站¹, 顾昌翰¹, 胡思前^1,²()

1. 江汉大学光电化学材料与器件教育部重点实验室, 武汉 430056
2. 化学与环境工程学院, 武汉 430056

收稿日期:2015-09-14 出版日期:2016-02-10 发布日期:2016-01-04
作者简介:联系人简介: 王亮, 男, 博士, 讲师, 主要从事杂环化合物的C—H官能化研究. E-mail:wangliang@jhun.edu.cn;胡思前, 男, 教授, 主要从事杂环导向的有机功能材料研究. E-mail:husiqian@126.com
基金资助:
国家自然科学基金(批准号: 21302064)、湖北省教育厅科学研究计划指导性项目(批准号: B2015231)和江汉大学博士科研启动经费项目(批准号: 2012023)资助

Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)₂^†

WANG Liang^1,^2,^*(), QU Xing¹, LI Zhan¹, GU Changhan¹, HU Siqian^1,^2,^*()

1. Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, Jianghan University, Wuhan 430056, China
2. School of Chemical and Enviromental Engineering, Jianghan University, Wuhan 430056, China

Received:2015-09-14 Online:2016-02-10 Published:2016-01-04
Contact: WANG Liang,HU Siqian E-mail:wangliang@jhun.edu.cn;husiqian@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21302064), the Scientific Research Project of Hubei Provincial Department of Education, China(No.B2015231) and the Scientific Research Initial Funds for Doctors of Jianghan University, China(No.2012023)

摘要/Abstract

摘要：

研究了无金属参与的二乙酸碘苯和吲哚的C3—H乙酸化反应, 通过对取代基效应、温度以及二乙酸碘苯用量等因素的考察, 建立了反应的最佳条件: 反应温度60 ℃, 乙酸(HOAc)为溶剂. 在无需任何添加剂条件下, 以中等到良好的收率获得一系列C3位乙酸化的吲哚衍生物. 采用红外光谱、核磁共振波谱、高分辨质谱及X射线单晶衍射分析对目标化合物进行了结构表征, 并推测了可能的反应机理. 该催化体系对于克量级规模反应均能获得很好的结果.

关键词: 无金属, 二乙酸碘苯, 吲哚, 乙酸化

Abstract:

3-Substituted indoles are common structural motifs in a series of natural products, pharmaceuticals and biologically active compounds. Metal-free reaction was emerged as one of the most powerful tools for functionalization of indoles due to its environment friendly features. In this work, the metal-free C3—H acetoxylation of indoles and PhI(OAc)₂ was developed. The optimized reaction conditions were established by examination of the substituent, temperature and amounts of PhI(OAc)₂. A series of 3-acetoxyindoles could be obtained in HOAc at 60 ℃ without additives. The yield of product ranged from 45% to 86%. The structures were characterized by infrared(IR), nuclear magnetion resonance(NMR), high resolution mass spectra(HRMS) and X-ray diffraction techniques and a possible reaction mechanism was then proposed. Moreover, this reaction system was also feasible in a gram-scale reaction without significant decrease in the product yields.

Key words: Metal-free, Diacetoxyiodobenzene, Indole, Acetoxylation

中图分类号:

O626.1

TrendMD:

王亮, 瞿星, 李站, 顾昌翰, 胡思前. 无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应. 高等学校化学学报, 2016, 37(2): 254.

WANG Liang, QU Xing, LI Zhan, GU Changhan, HU Siqian. Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)₂^†. Chem. J. Chinese Universities, 2016, 37(2): 254.

图/表 7

Scheme 1 Synthetic route for C3—H acetoxylation of indoles 2a: R1=H, R2=H; 2b: R1=4-Me, R2=H; 2c: R1=4-OBn, R2=H; 2d: R1=4-Cl, R2=H; 2e: R1=4-CO2Me, R2=H; 2f: R1=5-Me, R2=H; 2g: R1=5-OMe, R2=H; 2h: R1=5-OBn, R2=H; 2i: R1=5-OPh, R2=H; 2j: R1=5-Cl, R2=H; 2k: R1=5-Br, R2=H; 2l: R1=6-Me, R2=H; 2m: R1=6-CO2Me, R2=H; 2n: R1=6-F, R2=H; 2o: R1=6-Cl, R2=H; 2p: R1=6-Br, R2=H; 2q: R1=5,6-Ph, R2=H; 2r: R1=H, R2=Me; 2s: R1=H, R2=Ph; 2t: R1=H, R2=Br

Table 1 Appearance, yields, melting points, HRMS and IR data of compounds 2a—2t

Compd.	Appearance	Yield^*(%)	m. p./℃	HRMS(calcd.), m/z [M+Na⁺]	IR(KBr), $ν ˙$ /cm^-1
2a	White solid	85	123—124	276.0747(276.0743)	3195, 1743, 1573, 1458, 1428, 1369, 1316, 1208, 1158, 1124, 1073,1015
2b	Yellow solid	76	143—144	290.0925(290.0900)	3203, 2923, 2854, 1753, 1568, 1433, 1354, 1300, 1198, 1147
2c	White solid	63	127—128	382.1155(382.1162)	3210, 1738, 1573, 1499, 1448, 1362, 1271, 1232, 1160, 1096, 1064, 913
2d	White solid	73	155—156	310.0352(310.0354)	3192, 1756, 1563, 1452, 1360, 1309, 1212, 1001, 891, 770
2e	White solid	75	134—135	334.0789(334.0798)	2955, 1749, 1713, 1570, 1357, 1283, 1190, 1091, 1020, 954, 902, 740
2f	White solid	78	165—166	290.0900(290.0900)	3201, 1746, 1581, 1456, 1426, 1353, 1202, 1147, 1122, 864
2g	Yellow solid	80	166—167	306.0849(306.0849)	3209, 1744, 1536, 1436, 1366, 1210, 1075, 1020, 905, 801, 766, 747
2h	White solid	65	166—167	382.1128(382.1162)	3194, 1749, 1576, 1479, 1453, 1296, 1203, 1078, 1013, 919
2i	White solid	86	139—140	368.1009(368.1006)	3219, 1747, 1565, 1471, 1421, 1361, 1289, 1198, 1072, 965, 922
2j	Yellowish solid	83	181—182	310.0335(310.0354)	3206, 1756, 1573, 1459, 1373, 1346, 1292, 1203, 1065
2k	Yellowish solid	85	182—183	353.9846(353.9846)	3023, 1787, 1735, 1456, 1353, 1147, 1014, 919, 855, 784
2l	White solid	83	153—154	290.0875(290.0900)	3195, 2971, 2856, 1742, 1573, 1436, 1368, 1321, 1212, 1131, 789
2m	Yellow solid	63	199—200	334.0896(334.0798)	3197, 1752, 1717, 1571, 1441, 1373, 1280, 1210, 1140, 1064, 990
2n	Reddish solid	77	167—168	294.0660(294.0649)	3197, 1745, 1575, 1441, 1370, 1208, 1104, 976, 905, 855, 792
2o	White solid	70	179—180	310.0339(310.0354)	3199, 1793, 1744, 1440, 1367, 1209, 1129, 1066, 957, 792, 506
2p	White solid	80	178—179	353.9838(353.9849)	3202, 1746, 1577, 1441, 1367, 1209, 1128, 1080, 1001, 954, 786
2q	White solid	45	155—157	326.0901(326.0900)	3211, 1746, 1571, 1459, 1427, 1363, 1297, 1220, 1130, 1023, 883, 775
2r	Yellowish solid	84	158—159	290.0900(290.0900)	3207, 1745, 1598, 1556, 1444, 1366, 1317, 1207, 1008, 742
2s	White solid	81	133—134	352.1062(352.1056)	3195, 1752, 1589, 1548, 1444, 1366, 1197, 1123, 1009, 887, 746
2t	White solid	72	182—183	353.9681(353.9849)	3199, 1746, 1598, 1557, 1440, 1317, 1207, 1116, 1010, 743

Table 1 Appearance, yields, melting points, HRMS and IR data of compounds 2a—2t

Compd.	Appearance	Yield^*(%)	m. p./℃	HRMS(calcd.), m/z [M+Na⁺]	IR(KBr), $ν ˙$ /cm^-1
2a	White solid	85	123—124	276.0747(276.0743)	3195, 1743, 1573, 1458, 1428, 1369, 1316, 1208, 1158, 1124, 1073,1015
2b	Yellow solid	76	143—144	290.0925(290.0900)	3203, 2923, 2854, 1753, 1568, 1433, 1354, 1300, 1198, 1147
2c	White solid	63	127—128	382.1155(382.1162)	3210, 1738, 1573, 1499, 1448, 1362, 1271, 1232, 1160, 1096, 1064, 913
2d	White solid	73	155—156	310.0352(310.0354)	3192, 1756, 1563, 1452, 1360, 1309, 1212, 1001, 891, 770
2e	White solid	75	134—135	334.0789(334.0798)	2955, 1749, 1713, 1570, 1357, 1283, 1190, 1091, 1020, 954, 902, 740
2f	White solid	78	165—166	290.0900(290.0900)	3201, 1746, 1581, 1456, 1426, 1353, 1202, 1147, 1122, 864
2g	Yellow solid	80	166—167	306.0849(306.0849)	3209, 1744, 1536, 1436, 1366, 1210, 1075, 1020, 905, 801, 766, 747
2h	White solid	65	166—167	382.1128(382.1162)	3194, 1749, 1576, 1479, 1453, 1296, 1203, 1078, 1013, 919
2i	White solid	86	139—140	368.1009(368.1006)	3219, 1747, 1565, 1471, 1421, 1361, 1289, 1198, 1072, 965, 922
2j	Yellowish solid	83	181—182	310.0335(310.0354)	3206, 1756, 1573, 1459, 1373, 1346, 1292, 1203, 1065
2k	Yellowish solid	85	182—183	353.9846(353.9846)	3023, 1787, 1735, 1456, 1353, 1147, 1014, 919, 855, 784
2l	White solid	83	153—154	290.0875(290.0900)	3195, 2971, 2856, 1742, 1573, 1436, 1368, 1321, 1212, 1131, 789
2m	Yellow solid	63	199—200	334.0896(334.0798)	3197, 1752, 1717, 1571, 1441, 1373, 1280, 1210, 1140, 1064, 990
2n	Reddish solid	77	167—168	294.0660(294.0649)	3197, 1745, 1575, 1441, 1370, 1208, 1104, 976, 905, 855, 792
2o	White solid	70	179—180	310.0339(310.0354)	3199, 1793, 1744, 1440, 1367, 1209, 1129, 1066, 957, 792, 506
2p	White solid	80	178—179	353.9838(353.9849)	3202, 1746, 1577, 1441, 1367, 1209, 1128, 1080, 1001, 954, 786
2q	White solid	45	155—157	326.0901(326.0900)	3211, 1746, 1571, 1459, 1427, 1363, 1297, 1220, 1130, 1023, 883, 775
2r	Yellowish solid	84	158—159	290.0900(290.0900)	3207, 1745, 1598, 1556, 1444, 1366, 1317, 1207, 1008, 742
2s	White solid	81	133—134	352.1062(352.1056)	3195, 1752, 1589, 1548, 1444, 1366, 1197, 1123, 1009, 887, 746
2t	White solid	72	182—183	353.9681(353.9849)	3199, 1746, 1598, 1557, 1440, 1317, 1207, 1116, 1010, 743

Table 2 1H NMR and 13C NMR data of compounds 2a—2t

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
2a	8.81(d,J=8.4 Hz, 1H), 8.67(d, J=4.8 Hz, 2H), 8.43(s, 1H), 7.56(d, J=7.8 Hz, 1H), 7.37(t, J=7.5 Hz, 1H), 7.29—7.25(m, 1H), 7.02(t, J=4.8 Hz, 1H), 2.40(s, 3H)	168.2, 158.1, 157.8, 133.5, 132.8, 124.6, 124.0, 122.2, 117.5, 116.4, 116.1, 114.6, 21.1
2b	8.73—8.59(m, 3H), 8.36(s, 1H), 7.24(dd, J=10.3, 5.1 Hz, 1H), 7.02—6.92(m, 2H), 2.63(s, 3H), 2.37(s, 3H)	168.7, 158.1, 157.7, 134.3, 133.2, 129.4, 124.5, 123.9, 122.7, 116.0, 114.8, 114.1, 29.7, 21.3, 18.8
2c	8.66(d,J=4.8 Hz, 2H), 8.44(d, J=8.4 Hz, 1H), 8.06(s, 1H), 7.54—7.48(m, 2H), 7.40(dd, J=9.7, 5.6, 1.4 Hz, 3H), 7.25(d, J=4.6 Hz, 1H), 7.02(t, J=4.8 Hz, 1H), 6.74(d, J=7.9 Hz, 1H), 5.11(s, 2H), 1.91(s, 3H)	169.8, 158.1, 157.7, 152.0, 136.9, 135.1, 133.2, 128.5, 128.4, 128.2, 125.4, 116.2, 114.5, 114.2, 110.0, 104.1, 70.4, 20.4
2d	8.79—8.72(m, 1H), 8.66—8.61(m, 2H), 8.27(d, J=2.0 Hz, 1H), 7.20(t, J=7.7 Hz, 2H), 7.02(t, J=4.8, 3.4 Hz, 1H), 2.39(s, 3H)	169.5, 158.1, 157.2, 134.6, 132.2, 125.0, 124.2, 123.3, 121.4, 116.9, 116.6, 115.3, 21.1
2e	9.12(d,J=8.5 Hz, 1H), 8.66(d, J=4.7 Hz, 2H), 8.31(s, 1H), 7.82(d, J=7.5 Hz, 1H), 7.37(t, J=8.0 Hz, 1H), 7.05(t, J=4.6 Hz, 1H), 3.91(d, J=13.3 Hz, 3H), 2.41(s, 3H)	170.1, 167.2, 158.2, 157.3, 134.5, 132.8, 125.4, 123.5, 123.0, 122.5, 120.7, 118.7, 116.7, 52.2, 21.0
2f	8.69—8.59(m, 3H), 8.36(s, 1H), 7.33(s, 1H), 7.18(d, J=8.5 Hz, 1H), 6.97(t, J=4.2 Hz, 1H), 2.47(s, 3H), 2.39(s, 3H)	168.2, 158.1, 157.7, 133.3, 131.7, 131.2, 126.1, 124.2, 117.2, 116.2, 115.9, 114.6, 21.4, 21.1
2g	8.66(dd,J=22.8, 6.8 Hz, 3H), 8.39(s, 1H), 6.98(d, J=8.2 Hz, 3H), 3.89(s, 3H), 2.40(s, 3H)	168.1, 158.1, 157.6, 155.6, 133.4, 127.8, 124.7, 117.5, 115.8, 115.1, 114.0, 99.4, 55.7, 21.1
2h	8.70(d,J=8.7 Hz, 1H), 8.63(d, J=4.7 Hz, 2H), 8.40(s, 1H), 7.49(d, J=7.5 Hz, 2H), 7.40(t, J=7.3 Hz, 2H), 7.36—7.30(m, 1H), 7.06(d, J=9.8 Hz, 2H), 6.98(t, J=4.6 Hz, 1H), 5.13(s, 2H), 2.39(s, 3H), 5.13(s, 2H), 2.39(s, 3H)	168.1, 158.1, 157.6, 154.8, 137.3, 133.4, 128.6, 127.9, 127.7, 124.7, 117.6, 115.9, 115.2, 114.5, 101.0, 70.6, 21.1
2i	8.83—8.76(m, 1H), 8.67(d, J=4.8 Hz, 2H), 8.46(s, 1H), 7.38—7.29(m, 2H), 7.20(d, J=2.4 Hz, 1H), 7.14—6.99(m, 5H), 2.35(s, 3H)	168.1, 158.6, 158.1, 157.6, 152.0, 133.3, 129.7, 129.5, 125.0, 122.5, 117.8, 117.6, 116.1, 115.7, 107.9, 21.0
2j	8.84—8.61(m, 3H), 8.44(s, 1H), 7.52(s, 1H), 7.36—7.24(m, 1H), 7.05(s, 1H), 2.39(s, 3H)	168.0, 158.2, 157.5, 132.6, 131.1, 127.9, 125.1, 124.8, 117.7, 117.1, 116.4, 115.9, 21.0
2k	8.67(t,J=7.2 Hz, 3H), 8.42(s, 1H), 7.68(s, 1H), 7.43(d, J=8.9 Hz, 1H), 7.04(t, J=4.7 Hz, 1H), 2.39(s, 3H)	168.0, 158.2, 157.4, 132.4, 131.4, 127.4, 125.6, 120.2, 118.1, 116.4, 115.7, 115.5, 21.0
2l	8.81—8.55(m, 3H), 8.34(s, 1H), 7.42(d, J=7.9 Hz, 1H), 7.09(d, J=7.8 Hz, 1H), 6.98(t, J=4.7 Hz, 1H), 2.53(s, 3H), 2.38(s, 3H)	168.2, 158.1, 157.8, 134.7, 133.6, 133.2, 123.8, 121.9, 117.1, 116.5, 115.9, 113.9, 22.2, 21.1
2m	9.50(s, 1H), 8.72(d,J=4.6 Hz, 2H), 8.58(s, 1H), 7.95(d, J=8.3 Hz, 1H), 7.59(d, J=8.3 Hz, 1H), 7.08(t, J=4.6 Hz, 1H), 3.98(s, 3H), 2.41(s, 3H)	168.1, 168.0, 167.9, 158.3, 157.4, 133.1, 132.1, 127.3, 126.3, 123.2, 118.6, 117.7, 117.2, 116.6, 52.2, 29.7, 21.0
2n	8.66(d,J=4.6 Hz, 2H), 8.57(d, J=11.0 Hz, 1H), 8.39(s, 1H), 7.52—7.38(m, 1H), 7.02(dd, J=11.8, 6.6 Hz, 2H), 2.39(s, 3H)	168.0, 162.3, 158.1, 157.5, 133.2, 132.8, 132.7, 120.5, 118.2, 118.1, 116.3, 114.7, 114.7, 110.7, 110.5, 103.9, 103.6
2o	8.86(s, 1H), 8.66(d,J=4.5 Hz, 2H), 8.40(s, 1H), 7.45(d, J=8.3 Hz, 1H), 7.24(t, J=8.2 Hz, 1H), 7.04(t, J=4.4 Hz, 1H), 2.38(s, 3H)	168.0, 158.1, 157.4, 133.2, 132.9, 130.5, 122.7, 122.5, 118.3, 116.6, 116.4, 115.0, 21.0
2p	9.03(s, 1H), 8.68(t,J=3.6 Hz, 2H), 8.41(s, 1H), 7.39(q, J=8.4 Hz, 2H), 7.14—6.96(m, 1H), 2.39(s, 3H)	168.1, 168.0, 158.2, 157.4, 133.2, 125.4, 122.9, 119.5, 118.6, 118.4, 116.5, 115.0, 21.0
2q	9.00(dd,J=9.2, 2.5 Hz, 1H), 8.70—8.73(m, 2H), 8.59(d, J=8.8 Hz, 2H), 7.94(d, J=8.0 Hz, 1H), 7.75(d, J=9.2 Hz, 1H), 7.62—7.56(m, 1H), 7.52—7.46(m, 1H), 7.06(s, 1H), 2.53(s, 3H)	168.0, 158.2, 157.8, 135.4, 130.3, 129.9, 128.4, 127.0, 126.1, 125.1, 124.3, 123.7, 117.1, 116.7, 116.6, 113.8, 21.6
2r	8.77(d,J=8.4 Hz, 1H), 8.47(s, 2H), 8.39(s, 1H), 7.55(d, J=7.8 Hz, 1H), 7.36(t, J=7.8 Hz, 1H), 7.24(t, J=7.5 Hz, 1H), 2.39(s, 3H), 2.27(s, 3H)	168.2, 158.0, 156.1, 133.1, 132.7, 125.1, 124.4, 123.8, 121.9, 117.4, 116.2, 114.7, 21.0, 15.0
2s	8.89—8.81(m, 3H), 8.47(s, 1H), 7.57(d, J=6.3 Hz, 3H), 7.50(t, J=7.5 Hz, 2H), 7.46—7.36(m, 2H), 7.27(t, J=8.1 Hz, 1H), 2.40(s, 3H)	168.1, 156.8, 156.0, 134.4, 133.6, 132.8, 129.4, 129.0, 128.4, 126.5, 124.7, 124.0, 122.3, 117.5, 116.4, 114.6, 21.0
2t	8.73—8.60(m, 3H), 8.34(s, 1H), 7.55(d, J=7.8 Hz, 1H), 7.36(t, J=7.8 Hz, 1H), 7.26(t, J=6.3 Hz, 1H), 2.39(s, 3H)	168.0, 158.5, 155.9, 133.9, 132.7, 124.9, 124.1, 122.5, 117.6, 116.4, 114.4, 113.0, 21.1

Table 2 1H NMR and 13C NMR data of compounds 2a—2t

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
2a	8.81(d,J=8.4 Hz, 1H), 8.67(d, J=4.8 Hz, 2H), 8.43(s, 1H), 7.56(d, J=7.8 Hz, 1H), 7.37(t, J=7.5 Hz, 1H), 7.29—7.25(m, 1H), 7.02(t, J=4.8 Hz, 1H), 2.40(s, 3H)	168.2, 158.1, 157.8, 133.5, 132.8, 124.6, 124.0, 122.2, 117.5, 116.4, 116.1, 114.6, 21.1
2b	8.73—8.59(m, 3H), 8.36(s, 1H), 7.24(dd, J=10.3, 5.1 Hz, 1H), 7.02—6.92(m, 2H), 2.63(s, 3H), 2.37(s, 3H)	168.7, 158.1, 157.7, 134.3, 133.2, 129.4, 124.5, 123.9, 122.7, 116.0, 114.8, 114.1, 29.7, 21.3, 18.8
2c	8.66(d,J=4.8 Hz, 2H), 8.44(d, J=8.4 Hz, 1H), 8.06(s, 1H), 7.54—7.48(m, 2H), 7.40(dd, J=9.7, 5.6, 1.4 Hz, 3H), 7.25(d, J=4.6 Hz, 1H), 7.02(t, J=4.8 Hz, 1H), 6.74(d, J=7.9 Hz, 1H), 5.11(s, 2H), 1.91(s, 3H)	169.8, 158.1, 157.7, 152.0, 136.9, 135.1, 133.2, 128.5, 128.4, 128.2, 125.4, 116.2, 114.5, 114.2, 110.0, 104.1, 70.4, 20.4
2d	8.79—8.72(m, 1H), 8.66—8.61(m, 2H), 8.27(d, J=2.0 Hz, 1H), 7.20(t, J=7.7 Hz, 2H), 7.02(t, J=4.8, 3.4 Hz, 1H), 2.39(s, 3H)	169.5, 158.1, 157.2, 134.6, 132.2, 125.0, 124.2, 123.3, 121.4, 116.9, 116.6, 115.3, 21.1
2e	9.12(d,J=8.5 Hz, 1H), 8.66(d, J=4.7 Hz, 2H), 8.31(s, 1H), 7.82(d, J=7.5 Hz, 1H), 7.37(t, J=8.0 Hz, 1H), 7.05(t, J=4.6 Hz, 1H), 3.91(d, J=13.3 Hz, 3H), 2.41(s, 3H)	170.1, 167.2, 158.2, 157.3, 134.5, 132.8, 125.4, 123.5, 123.0, 122.5, 120.7, 118.7, 116.7, 52.2, 21.0
2f	8.69—8.59(m, 3H), 8.36(s, 1H), 7.33(s, 1H), 7.18(d, J=8.5 Hz, 1H), 6.97(t, J=4.2 Hz, 1H), 2.47(s, 3H), 2.39(s, 3H)	168.2, 158.1, 157.7, 133.3, 131.7, 131.2, 126.1, 124.2, 117.2, 116.2, 115.9, 114.6, 21.4, 21.1
2g	8.66(dd,J=22.8, 6.8 Hz, 3H), 8.39(s, 1H), 6.98(d, J=8.2 Hz, 3H), 3.89(s, 3H), 2.40(s, 3H)	168.1, 158.1, 157.6, 155.6, 133.4, 127.8, 124.7, 117.5, 115.8, 115.1, 114.0, 99.4, 55.7, 21.1
2h	8.70(d,J=8.7 Hz, 1H), 8.63(d, J=4.7 Hz, 2H), 8.40(s, 1H), 7.49(d, J=7.5 Hz, 2H), 7.40(t, J=7.3 Hz, 2H), 7.36—7.30(m, 1H), 7.06(d, J=9.8 Hz, 2H), 6.98(t, J=4.6 Hz, 1H), 5.13(s, 2H), 2.39(s, 3H), 5.13(s, 2H), 2.39(s, 3H)	168.1, 158.1, 157.6, 154.8, 137.3, 133.4, 128.6, 127.9, 127.7, 124.7, 117.6, 115.9, 115.2, 114.5, 101.0, 70.6, 21.1
2i	8.83—8.76(m, 1H), 8.67(d, J=4.8 Hz, 2H), 8.46(s, 1H), 7.38—7.29(m, 2H), 7.20(d, J=2.4 Hz, 1H), 7.14—6.99(m, 5H), 2.35(s, 3H)	168.1, 158.6, 158.1, 157.6, 152.0, 133.3, 129.7, 129.5, 125.0, 122.5, 117.8, 117.6, 116.1, 115.7, 107.9, 21.0
2j	8.84—8.61(m, 3H), 8.44(s, 1H), 7.52(s, 1H), 7.36—7.24(m, 1H), 7.05(s, 1H), 2.39(s, 3H)	168.0, 158.2, 157.5, 132.6, 131.1, 127.9, 125.1, 124.8, 117.7, 117.1, 116.4, 115.9, 21.0
2k	8.67(t,J=7.2 Hz, 3H), 8.42(s, 1H), 7.68(s, 1H), 7.43(d, J=8.9 Hz, 1H), 7.04(t, J=4.7 Hz, 1H), 2.39(s, 3H)	168.0, 158.2, 157.4, 132.4, 131.4, 127.4, 125.6, 120.2, 118.1, 116.4, 115.7, 115.5, 21.0
2l	8.81—8.55(m, 3H), 8.34(s, 1H), 7.42(d, J=7.9 Hz, 1H), 7.09(d, J=7.8 Hz, 1H), 6.98(t, J=4.7 Hz, 1H), 2.53(s, 3H), 2.38(s, 3H)	168.2, 158.1, 157.8, 134.7, 133.6, 133.2, 123.8, 121.9, 117.1, 116.5, 115.9, 113.9, 22.2, 21.1
2m	9.50(s, 1H), 8.72(d,J=4.6 Hz, 2H), 8.58(s, 1H), 7.95(d, J=8.3 Hz, 1H), 7.59(d, J=8.3 Hz, 1H), 7.08(t, J=4.6 Hz, 1H), 3.98(s, 3H), 2.41(s, 3H)	168.1, 168.0, 167.9, 158.3, 157.4, 133.1, 132.1, 127.3, 126.3, 123.2, 118.6, 117.7, 117.2, 116.6, 52.2, 29.7, 21.0
2n	8.66(d,J=4.6 Hz, 2H), 8.57(d, J=11.0 Hz, 1H), 8.39(s, 1H), 7.52—7.38(m, 1H), 7.02(dd, J=11.8, 6.6 Hz, 2H), 2.39(s, 3H)	168.0, 162.3, 158.1, 157.5, 133.2, 132.8, 132.7, 120.5, 118.2, 118.1, 116.3, 114.7, 114.7, 110.7, 110.5, 103.9, 103.6
2o	8.86(s, 1H), 8.66(d,J=4.5 Hz, 2H), 8.40(s, 1H), 7.45(d, J=8.3 Hz, 1H), 7.24(t, J=8.2 Hz, 1H), 7.04(t, J=4.4 Hz, 1H), 2.38(s, 3H)	168.0, 158.1, 157.4, 133.2, 132.9, 130.5, 122.7, 122.5, 118.3, 116.6, 116.4, 115.0, 21.0
2p	9.03(s, 1H), 8.68(t,J=3.6 Hz, 2H), 8.41(s, 1H), 7.39(q, J=8.4 Hz, 2H), 7.14—6.96(m, 1H), 2.39(s, 3H)	168.1, 168.0, 158.2, 157.4, 133.2, 125.4, 122.9, 119.5, 118.6, 118.4, 116.5, 115.0, 21.0
2q	9.00(dd,J=9.2, 2.5 Hz, 1H), 8.70—8.73(m, 2H), 8.59(d, J=8.8 Hz, 2H), 7.94(d, J=8.0 Hz, 1H), 7.75(d, J=9.2 Hz, 1H), 7.62—7.56(m, 1H), 7.52—7.46(m, 1H), 7.06(s, 1H), 2.53(s, 3H)	168.0, 158.2, 157.8, 135.4, 130.3, 129.9, 128.4, 127.0, 126.1, 125.1, 124.3, 123.7, 117.1, 116.7, 116.6, 113.8, 21.6
2r	8.77(d,J=8.4 Hz, 1H), 8.47(s, 2H), 8.39(s, 1H), 7.55(d, J=7.8 Hz, 1H), 7.36(t, J=7.8 Hz, 1H), 7.24(t, J=7.5 Hz, 1H), 2.39(s, 3H), 2.27(s, 3H)	168.2, 158.0, 156.1, 133.1, 132.7, 125.1, 124.4, 123.8, 121.9, 117.4, 116.2, 114.7, 21.0, 15.0
2s	8.89—8.81(m, 3H), 8.47(s, 1H), 7.57(d, J=6.3 Hz, 3H), 7.50(t, J=7.5 Hz, 2H), 7.46—7.36(m, 2H), 7.27(t, J=8.1 Hz, 1H), 2.40(s, 3H)	168.1, 156.8, 156.0, 134.4, 133.6, 132.8, 129.4, 129.0, 128.4, 126.5, 124.7, 124.0, 122.3, 117.5, 116.4, 114.6, 21.0
2t	8.73—8.60(m, 3H), 8.34(s, 1H), 7.55(d, J=7.8 Hz, 1H), 7.36(t, J=7.8 Hz, 1H), 7.26(t, J=6.3 Hz, 1H), 2.39(s, 3H)	168.0, 158.5, 155.9, 133.9, 132.7, 124.9, 124.1, 122.5, 117.6, 116.4, 114.4, 113.0, 21.1

Table 3 Optimization of the reaction conditionsa

Entry	R	T/℃	Molar fraction(%)	Yield^b(%)	Entry	R	T/℃	Molar fraction(%)	Yield^b(%)
1	H	50	150	0	10	2-Pyrimidyl	25	150	0
2	Me	50	150	0	11	2-Pyrimidyl	40	150	45
3	Bn	50	150	0	12	2-Pyrimidyl	60	150	85
4	Ph	50	150	40	13	2-Pyrimidyl	70	150	83
5	2-Py	50	150	65	14	2-Pyrimidyl	80	150	80
6	2-Pyrimidyl	50	150	78	15	2-Pyrimidyl	60	110	83
7	Ac	50	150	0	16	2-Pyrimidyl	60	120	85
8	Boc	50	150	0	17	2-Pyrimidyl	60	200	80
9	PhSO₂	50	150	0	18	2-Pyrimidyl	60	250	76

Table 4 Substrate scope of the C3—H acetoxylation of indoles

Entry	Product	R¹	R²	Yield^*(%)	Entry	Product	R¹	R²	Yield^*(%)
1	2a	H	H	85	11	2k	5-Br	H	85
2	2b	4-Me	H	76	12	2l	6-Me	H	83
3	2c	4-OBn	H	63	13	2m	6-CO₂Me	H	63
4	2d	4-Cl	H	73	14	2n	6-F	H	77
5	2e	4-CO₂Me	H	75	15	2o	6-Cl	H	70
6	2f	5-Me	H	78	16	2p	6-Br	H	80
7	2g	5-OMe	H	80	17	2q	5,6-Ph	H	45
8	2h	5-OBn	H	65	18	2r	H	Me	84
9	2i	5-OPh	H	86	19	2s	H	Ph	81
10	2j	5-Cl	H	83	20	2t	H	Br	72

Fig.1 Crystal structure of compound 2a

Scheme 2 Proposed mechanism of the C3—H acetoxylation of indoles

参考文献 25

[1]	Cacchi S., Fabrizi G., Chem. Rev., 2005, 105(7), 2873—2920
[2]	Kang C. M., Zhao X. H., Yu Y. Q., Lü Y. T., Chem. J. Chinese Universities, 2014, 35(3), 550—554
	(康从民, 赵绪浩, 于玉琪, 吕英涛. 高等学校化学学报, 2014, 35(3), 550—554)
[3]	Zhang J. H., Lü Y., Jia H. L., Song Y. Y., Sun X. X., Chai D. X., Wang L. Y., Chem. J. Chinese Universities, 2015, 36(10), 1924—1932
	(张江华, 吕英, 贾红亮, 宋银银, 孙晓霞, 柴敦宵, 王兰英. 高等学校化学学报, 2015, 36(10), 1924—1932)
[4]	Cheng X., Li X. L., Wan W. L., Hao W. M., Hai L., Wu Y., Chem. Res. Chinese Universities, 2015, 31(1), 53—59
[5]	Li X. L., Qiu R., Wan W. L., Cheng X., He Y., Hai L., Wu Y., Chem. Res. Chinese Universities, 2015, 31(4), 539—542
[6]	Guyen B., Schultes C. M., Hazel P., Mann J., Neidle S., Org. Biomol. Chem., 2004, 2(7), 981—988
[7]	Arnold R. D., Nutter W. M., Stepp W. L., J. Org. Chem., 1959, 24(1), 117—118
[8]	Bandini M., Eichholzer A., Angew. Chem. Int. Ed., 2009, 48(51), 9608—9644
[9]	Chen J. R., Li C. F., An X. L., Zhang J. J., Zhu X.Y., Xiao W. J., Angew. Chem. Int. Ed., 2008, 47(13), 2489—2492
[10]	An X. L., Chen J. R., Li C. F., Zhang F. G., Zou Y. Q., Guo Y. C., Xiao W. J., Chem. Asian J., 2010, 5(10), 2258—2265
[11]	Cho S. H., Kim J. Y., Kwak J., Chang S., Chem. Soc. Rev., 2011, 40(10), 5068—5083
[12]	Stuart D. R., Fagnou K., Science, 2007, 316(5), 1172—1175
[13]	Liu H. H., Wang Y., Deng G., Yang L., Adv. Synth. Catal., 2013, 355(17), 3369—3374
[14]	Li Y. X., Wang H. X., Ali S., Xia X. F., Liang Y. M., Chem. Commun., 2012, 48(17), 2343—2345
[15]	Liu Q., Li G., Yi H., Wu P., Liu J., Lei A., Chem. Eur. J., 2011, 17(8), 2353—2357
[16]	Sun C. L., Shi Z. J., Chem. Rev., 2014, 114(18), 9219—9280
[17]	Allais C., Grassot J. M., Rodriguez J., Constantieux T., Chem. Rev., 2014, 114(21), 10829—10868
[18]	Zhdankin V. V., Stang P. J., Chem. Rev., 2002, 102(7), 2523—2584
[19]	Wirth T., Angew. Chem. Int. Ed., 2005, 44(24), 3656—3665
[20]	Cho S. H., Yoon J., Chang S., J. Am. Chem. Soc., 2011, 133(15), 5996—6005
[21]	Liu K., Wen P., Liu J., Huang G., Synthesis, 2010, 21, 3623—3626
[22]	Ackermann L., Dell’Acqua M., Fenner S., Vicente R., Sandmann R., Org. Lett., 2011, 13(9), 2358—2360
[23]	Wen J., Zhang R. Y., Chen S. Y., Zhang J., Yu X. Q., J. Org. Chem., 2012, 77(1), 766—771
[24]	Wang L., Qu X., Li Z., Peng W. M., Tetrahedron Lett., 2015, 56(24), 3754—3757
[25]	Wang L., Qu X., Li Z., Peng W. M., Chin. J. Org. Chem., 2015, 35(3), 688—697
	(王亮, 瞿星, 李站, 彭望明. 有机化学, 2015, 35(3), 688—697)

无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应

Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)₂^†

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无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应

Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)2†

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Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)₂^†