以芳基碘为碘化试剂的苯酚衍生物的位点选择性C—H键碘化反应

doi:10.6023/cjoc202106011

有机化学 ›› 2021, Vol. 41 ›› Issue (9): 3511-3520.DOI: 10.6023/cjoc202106011 上一篇下一篇

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研究论文

以芳基碘为碘化试剂的苯酚衍生物的位点选择性C—H键碘化反应

张涛^a, 李尚达^b^,^*(), 周春林^b, 王新超^b, 张孟^b, 高泽众^b, 李纲^b^,^*()

a 中北大学理学院山西太原 030051
b 中国科学院福建物质结构研究所煤制乙二醇及相关技术重点实验室福州 350002

收稿日期:2021-06-06 修回日期:2021-06-07 发布日期:2021-06-07
通讯作者: 李尚达, 李纲
基金资助:
国家自然科学基金(22022111); 国家自然科学基金(22071248); 福建省自然科学基金(2020J02008); 福建省自然科学基金(2020J01108); 中国科学院青年创新促进会(2020306)

Site-Selective C—H Iodination of Phenol Derivatives Using Aryl Iodide as Iodinating Reagent

Tao Zhang^a, Shangda Li^b(), Chunlin Zhou^b, Xinchao Wang^b, Meng Zhang^b, Zezhong Gao^b, Gang Li^b()

a School of Science, North University of China, Taiyuan, Shanxi 030051
b Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

Received:2021-06-06 Revised:2021-06-07 Published:2021-06-07
Contact: Shangda Li, Gang Li
Supported by:
National Natural Science Foundation of China(22022111); National Natural Science Foundation of China(22071248); Natural Science Foundation of Fujian Province(2020J02008); Natural Science Foundation of Fujian Province(2020J01108); Youth Innovation Promotion Association of the Chinese Academy of Sciences(2020306)

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摘要/Abstract

富电子苯酚类化合物的位点选择性C—H键碘化是一个挑战性的反应. 报道了一类钯催化的、利用4-碘基-3-硝基苯甲醚为温和的碘化试剂, 实现无保护2-芳基苯酚和2-苯氧乙酸类化合物的C—H键碘化反应. 该反应适用于一系列富电子的苯酚类衍生物, 且能够获得优秀的位点选择性和良好的官能团耐受性. 结果表明, 对于具有挑战性底物的C—H键碘化, 经由形式复分解的C—H键碘化反应是一个潜在的有用方法.

关键词: C—H键碘化, 形式复分解, 位点选择性, 苯酚, 芳基碘化物, 钯催化

Site-selective C—H iodination of electron-rich phenols is a challenging reaction. A Pd(II)-catalyzed C—H iodination of free 2-aryl phenols and 2-phenoxyacetic acids using 4-iodo-3-nitroanisole as the mild iodinating reagent was reported. Excellent site-selectivity and good functional group tolerance were obtained with a range of electron rich phenol derivatives. These results suggest that C—H iodination via formal metathesis is a potentially useful method for C—H iodination of challenging substrates.

Key words: C—H iodination, formal metathesis, site-selectivity, phenol, aryl iodide, palladium catalysis

引用此文

张涛, 李尚达, 周春林, 王新超, 张孟, 高泽众, 李纲. 以芳基碘为碘化试剂的苯酚衍生物的位点选择性C—H键碘化反应[J]. 有机化学, 2021, 41(9): 3511-3520.

Tao Zhang, Shangda Li, Chunlin Zhou, Xinchao Wang, Meng Zhang, Zezhong Gao, Gang Li. Site-Selective C—H Iodination of Phenol Derivatives Using Aryl Iodide as Iodinating Reagent[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3511-3520.

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参考文献 16

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Entry	Ligand	Base (equiv.)	Ag salt (equiv.)	T/℃	Yield/% 2a/3a	Entry	Ligand	Base (equiv.)	Ag salt (equiv.)	T/℃	Yield/% 2a/3a
1	L1	NaOAc (0.5)	—	90	23/10	12	L3	K₂CO₃ (1.0)	AgNO₃ (0.1)	90	50/7
2	L2	NaOAc (0.5)	—	90	47/8	13	L3	K₂CO₃ (1.0)	AgBr (0.1)	90	65/6
3	L3	NaOAc (0.5)	—	90	52/10	14	L3	K₂CO₃ (1.0)	AgCl (0.2)	90	80/8
4	L3	NaOAc (1.0)	—	90	57/9	15	L3	K₂CO₃ (1.0)	AgCl (0.5)	90	66/8
5	L3	Na₂CO₃ (1.0)	—	90	73/10	16	L3	K₂CO₃ (1.0)	AgCl (0.1)	80	82/8
6	L3	K₂CO₃ (1.0)	—	90	77/7	17	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	81/8
7	L3	K₂CO₃ (2.0)	—	90	72/10	18^b	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	80/8
8	L3	KOH (1.0)	—	90	69/6	19^c	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	82/7
9	L3	K₂CO₃ (1.0)	AgCl (0.1)	90	82/8	20^d	L2	K₂CO₃ (1.0)	AgCl (0.1)	60	25/1
10	L3	K₂CO₃ (1.0)	AgOAc (0.1)	90	50/5	21^e	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	85/7^f
11	L2	K₂CO₃ (1.0)	Ag₂CO₃ (0.1)	90	63/7	22^g	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	65/5

Entry	Ligand	Base (equiv.)	Ag salt (equiv.)	T/℃	Yield/% 2a/3a	Entry	Ligand	Base (equiv.)	Ag salt (equiv.)	T/℃	Yield/% 2a/3a
1	L1	NaOAc (0.5)	—	90	23/10	12	L3	K₂CO₃ (1.0)	AgNO₃ (0.1)	90	50/7
2	L2	NaOAc (0.5)	—	90	47/8	13	L3	K₂CO₃ (1.0)	AgBr (0.1)	90	65/6
3	L3	NaOAc (0.5)	—	90	52/10	14	L3	K₂CO₃ (1.0)	AgCl (0.2)	90	80/8
4	L3	NaOAc (1.0)	—	90	57/9	15	L3	K₂CO₃ (1.0)	AgCl (0.5)	90	66/8
5	L3	Na₂CO₃ (1.0)	—	90	73/10	16	L3	K₂CO₃ (1.0)	AgCl (0.1)	80	82/8
6	L3	K₂CO₃ (1.0)	—	90	77/7	17	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	81/8
7	L3	K₂CO₃ (2.0)	—	90	72/10	18^b	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	80/8
8	L3	KOH (1.0)	—	90	69/6	19^c	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	82/7
9	L3	K₂CO₃ (1.0)	AgCl (0.1)	90	82/8	20^d	L2	K₂CO₃ (1.0)	AgCl (0.1)	60	25/1
10	L3	K₂CO₃ (1.0)	AgOAc (0.1)	90	50/5	21^e	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	85/7^f
11	L2	K₂CO₃ (1.0)	Ag₂CO₃ (0.1)	90	63/7	22^g	L3	K₂CO₃ (1.0)	AgCl (0.1)	60	65/5

以芳基碘为碘化试剂的苯酚衍生物的位点选择性C—H键碘化反应

Site-Selective C—H Iodination of Phenol Derivatives Using Aryl Iodide as Iodinating Reagent

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