醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

doi:10.6023/cjoc202009030

有机化学 ›› 2021, Vol. 41 ›› Issue (3): 1098-1107.DOI: 10.6023/cjoc202009030 上一篇下一篇

研究论文

醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

王涛^a^,^b^,^*(), 王晓莎^a, 宋雅雯^a, 霍晶晶^a, 周敬栓^a, 康庆伟^a, 刘澜涛^a^,^b^,^c^,^*()

a 商丘师范学院化学化工学院药物绿色合成河南省工程实验室河南商丘 476000
b 商丘师范学院化学化工学院河南省生物分子识别与传感重点实验室河南商丘 476000
c 郑州大学化学学院郑州 450001

收稿日期:2020-09-12 修回日期:2020-09-30 发布日期:2020-10-22
通讯作者: 王涛, 刘澜涛
基金资助:
河南省高等学校重点科研(19A150035); 河南省科技攻关(192102110222); 河南省高校科技创新人才基金(14HASTIT016); 河南省科技创新杰出人才基金(184100510011)

Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

Tao Wang^a^,^b^,^*(), Xiaosha Wang^a, Yawen Song^a, Jingjing Huo^a, Jingshuan Zhou^a, Qingwei Kang^a, Lantao Liu^a^,^b^,^c^,^*()

a Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
b Henan Key Laboratory of Biomolecular Recognition and Sensing, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
c College of Chemistry, Zhengzhou University, Zhengzhou 450001

Received:2020-09-12 Revised:2020-09-30 Published:2020-10-22
Contact: Tao Wang, Lantao Liu
About author:
* Corresponding authors. E-mail: wt67751726@126.com;
liult05@iccas.ac.cn
Supported by:
Key Science Research of Education Committee in Henan Province(19A150035); Key Scienti?c and Technological Project of Henan Province(192102110222); Program for Science & Technology Innovation Talents in Universities of Henan Province(14HASTIT016); Program of Science and Technology Innovation Talents of Henan Province(184100510011)

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1. cjoc202009030辅助材料.pdf(22343KB)

摘要/Abstract

以酰胺-噁唑啉为辅助基团, 在廉价的醋酸铜促进下, 实现了酰胺衍生物C(sp²)—H键与芳基硫醇S—H键的脱氢偶联反应; 以中等到优秀的产率(最高可达90%)简单高效地合成了一系列双硫化的酰胺衍生物. 值得一提的是, 底物范围并不局限于各种取代苯基酰胺化合物, 吡啶基酰胺化合物也可以兼容. 该反应的特点是: 金属廉价、底物范围广、反应条件温和、无需外加配体、空气作为氧化剂、区域选择性好(仅酰胺基团邻位的C—H键发生反应, 而噁唑啉基团邻位的C—H键不发生反应); 此外, 克级规模的反应表明了其在合成中的实用性.

关键词: 铜, C—H键, 硫代化, 酰胺-噁唑啉, 芳基硫醇

An efficient copper-mediated dithiolation of C(sp²)—H bonds with aryl thiols was achieved by using amide-oxazo- line as directing group. This strategy gives a variety of functionalized thioethers in moderate to excellent yields (up to 90%) in simple and efficient way. Importantly, the substrate scope is not limited to various substituted phenylamides, and diverse pyridine amides are also compatible. Furthermore, the protocol has been successfully implemented for the gram-scale synthesis as well.

Key words: copper, C—H bond, thiolation, amide-oxazoline, aryl thiols

引用此文

王涛, 王晓莎, 宋雅雯, 霍晶晶, 周敬栓, 康庆伟, 刘澜涛. 醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究[J]. 有机化学, 2021, 41(3): 1098-1107.

Tao Wang, Xiaosha Wang, Yawen Song, Jingjing Huo, Jingshuan Zhou, Qingwei Kang, Lantao Liu. Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1098-1107.

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图/表 7

图1. 具有芳基硫醚骨架的药物分子

Figure 1. Drugs containing aryl thioethers skeleton

图式1. 铜(II)促进的C—H键双硫代化反应

Scheme 1. Cu(II)-mediated C—H bond dhiolation.

Entry	Reagent	Base	Temp./℃	Yield^b/%
1	Cu(OAc)₂	NaOAc	100	84
2	Cu(OAc)₂	KOAc	100	20
3	Cu(OAc)₂	CsOAc	100	30
4	Cu(OAc)₂	K₂CO₃	100	24
5	Cu(OAc)₂	Na₂CO₃	100	8
6	Cu(OAc)₂	Cs₂CO₃	100	Trace
7	Cu(OAc)₂	NaHCO₃	100	26
8	Cu(OAc)₂	K₃PO₄	100	15
9	Cu(OAc)₂	NaOAc	120	76
10	Cu(OAc)₂	NaOAc	80	90
11	Cu(OAc)₂	NaOAc	60	59
12	Cu(OAc)₂?H₂O	NaOAc	80	82
13	Co(OAc)₂	NaOAc	80	—
14	Cu(OAc)₂?4H₂O	NaOAc	80	—
15^c	Cu(OAc)₂	NaOAc	80	30
16^d	Cu(OAc)₂	NaOAc	80	73

表1. 反应条件筛选a

Table 1. Optimization of the reaction conditionsa

表2. 各种取代苯基酰胺类化合物底物拓展a

Table 2. Scope of the reaction in terms of various substituted phenylamidesa

表3. 芳基硫醇类化合物底物拓展a

Table 3. Scope of the reaction in terms of aryl thiolsa

表4. 吡啶基酰胺类化合物底物拓展a

Table 4. Scope of the reaction in terms of diverse pyridine amidesa

图式2. 克级规模合成

Scheme 2. Gram-scale synthesis

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醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

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醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

Cu(OAc)2-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

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Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols