多功能氧酰胺导向基在碳氢键活化反应中的研究进展

引用本文: 朱月路, 赵鑫阳, 吴谦, 陈颖, 赵劲. 多功能氧酰胺导向基在碳氢键活化反应中的研究进展[J]. 物理化学学报, 2019, 35(9): 989-1004. doi: 10.3866/PKU.WHXB201812016 shu

Citation: ZHU Yuelu, ZHAO Xinyang, WU Qian, CHEN Ying, ZHAO Jing. Research Advances in C―H Bond Activation of Multitasking N-Phenoxyamides[J]. Acta Physico-Chimica Sinica, 2019, 35(9): 989-1004. doi: 10.3866/PKU.WHXB201812016 shu

多功能氧酰胺导向基在碳氢键活化反应中的研究进展

朱月路 ^1, ,
赵鑫阳 ^1, ,
吴谦 ^2, ,
陈颖 ^2, ,
赵劲 ^{1,
,}

1.
配位化学国家重点实验室，化学和生物医学科学研究所，南京大学化学与化工学院，南京 210093
2.
广东省纳米材料研究重点实验室，北京大学深圳研究生院化学生物学与生物技术学院，广东深圳 518055

作者简介:

赵劲，出生于1978年。2005年获得美国耶鲁大学博士学位，随后赴加州大学伯克利分校和芝加哥大学进行博士后研究。2007年–2008年在美国罗门哈斯公司担任高级研究员。2008年–2014年南京大学生命科学学院教授。2014年起任南京大学化学化工学院教授。主要从事金属蛋白和金属酶的结构、生物相容的金属催化反应和荧光小分子探针的研究;

通讯作者: 赵劲, jingzhao@nju.edu.cn

基金项目:
国家自然科学基金(21622103, 21571098, 91753121), 江苏省自然科学基金(BK20160022), 深圳基础研究项目(JCYJ20170413150538897), 中央大学基础研究经费(020514380139)资助项目

摘要: 近年来，通过导向基团进行碳氢键活化构建C―C键及C―X键的方法得到了快速发展，已成为有机合成的重要手段之一。在碳氢键活化中，作为多功能导向基团之一的氧酰胺，由于其独特的性质，引起了科学家们的广泛关注。氧酰胺中O―N键的氧化性替代外部氧化剂，使反应处于氧化还原中性。加入化学计量的外部氧化剂，通常可以使O―N键得到保留。在不同的溶剂中，能够表现出不同的区域选择性和立体选择性；皆体现了氧酰胺作为导向基团的独特之处。本文综述了N-苯氧基酰胺作为底物进行碳氢键活化的研究进展，同时根据现有的实验和理论研究结果对不同反应的机理进行了探讨。

关键词:

English

Research Advances in C―H Bond Activation of Multitasking N-Phenoxyamides

ZHU Yuelu ^1, ,
ZHAO Xinyang ^1, ,
WU Qian ^2, ,
CHEN Ying ^2, ,
ZHAO Jing ^{1,
,}

1.
State Key Laboratory of Coordination Chemistry, Institute of Chemistry and BioMedical Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China
2.
Guangdong Key Lab of Nano-Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, Guangdong Province, P. R. China

Corresponding author: ZHAO Jing, Email: jingzhao@nju.edu.cn; Tel.: +86-25-89681978

Received Date: 05 December 2018
Accepted Date: 15 January 2019
Revised Date: 15 January 2019
Available Online: 15 September 2019
Fund Project:
The project was supported by the National Science Foundation of China (21622103, 21571098, 91753121), Natural Science Foundation of Jiangsu Province, China (BK20160022), Shenzhen Basic Research Program, China (JCYJ20170413150538897), and Fundamental Research Funds for the Central Universities, China (020514380139)

Abstract: Transition-metal-catalyzed C―H functionalization reactions, assisted by directing groups (DGs), have become some of the most powerful strategies to form C―C and C―X (X = O, N, S, etc.) bonds. It has brought about a revolution in the synthesis of drugs and natural products, and the method is widely applicable in the fields of material chemistry and pharmaceutical industry. This strategy has mainly focused on regioselective C―H functionalization of amides, esters, carbamates, and enamides with DGs to form C―C and C―X bonds. Since these DGs are relatively stable, they must be removed by other methods when the reaction is completed. Therefore, the use of a traceless DG is one of the important challenges for transition-metal-catalyzed C―H functionalization. Recently, N-phenoxyamide has been attracting significant research attention as a versatile DG. Oxyacetamide (O―NHAc) is one of the most versatile functionalities for directed C―H functionalization cascades, such as the internal oxidation with N―O bond cleavage. The O―NHAc has been reported as a superb DG for redox-neutral C―H activation/annulation cascade reactions to synthesize phenol and complex heterocyclic scaffolds by coupling with alkynes, alkenes, heteroarenes, and diazo compounds. However, for the external oxidation with preservation of the N―O bond, e.g. when a stoichiometric external oxidant is present, N-phenoxyamides could react with aldehydes or α, β-unsaturated aldehydes. In addition, the solvent can control the chemoselectivity. In this minireview, the C―H bond functionalization of N-phenoxyamide is divided into five categories according to the different substrates, viz. alkenes, alkynes, diazo, and other compounds and intramolecular C―H bond activation reactions. Based on experimental and theoretical research results, the reaction mechanism was discussed. In the first part, we summarize the ortho-alkylation, alkenylation, and cyclization of N-phenoxyamide with olefins. In the second part, we present the Rh- and Ir-catalyzed C―H activation or cyclization of N-phenoxyamide with alkanes to synthesize phenol or benzofuran compounds. In the third part, we describe the synthesis of phenolic compounds functionalized by Rh-catalyzed diazo compounds by carbene intermediates and N-phenoxyamides. The forth part summarizes the C―H activation/annulation reaction using aldehydes, heterocyclic aromatic, and sulfur reagents as substrates. The last part of the paper generalizes the intramolecular ortho-hydroxylation and ortho, para-amidation reactions.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

多功能氧酰胺导向基在碳氢键活化反应中的研究进展

通讯作者: 赵劲, jingzhao@nju.edu.cn

English

Research Advances in C―H Bond Activation of Multitasking N-Phenoxyamides

Corresponding author: ZHAO Jing, Email: jingzhao@nju.edu.cn; Tel.: +86-25-89681978

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

多功能氧酰胺导向基在碳氢键活化反应中的研究进展

通讯作者: 赵劲, jingzhao@nju.edu.cn

English

Research Advances in C―H Bond Activation of Multitasking N-Phenoxyamides

Corresponding author: ZHAO Jing, Email: jingzhao@nju.edu.cn; Tel.: +86-25-89681978

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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