碘(III)介导的碳自由基参与的氧化偶联反应

doi:10.6023/cjoc202109012

有机化学 ›› 2022, Vol. 42 ›› Issue (3): 884-890.DOI: 10.6023/cjoc202109012 上一篇下一篇

研究论文

碘(III)介导的碳自由基参与的氧化偶联反应

吴福芳, 李雪健, 贾浩, 韩宣振, 沈晓宝^*()

阜阳师范大学生物质转化与污染防控安徽省高校工程技术研究中心安徽阜阳 236037

收稿日期:2021-09-06 修回日期:2021-10-11 发布日期:2021-11-03
通讯作者: 沈晓宝
基金资助:
国家自然科学基金(21602029); 安徽省高校优秀人才支持计划重点(gxyqZD2020030); 安徽省教育厅自然科学重点(KJ2020A0526); 阜阳市政府-阜阳师范学院横向合作科研(XDHX201722); 安徽省科技重大专项(18030701213)

Iodine(III)-Promoted Oxidative Cross-Coupling Reactions of C—H Bonds via a Free Radical Process

Fufang Wu, Xuejian Li, Hao Jia, Xuanzhen Han, Xiaobao Shen()

Engineering Research Center of Biomass Conversion and Pollution Prevention of Anhui Educational Institutions, Fuyang Normal University, Fuyang, Anhui 236037

Received:2021-09-06 Revised:2021-10-11 Published:2021-11-03
Contact: Xiaobao Shen
Supported by:
National Natural Science Foundation of China(21602029); Natural Science Foundation of Higher Education Institutions in Anhui Province(gxyqZD2020030); Key Projects of the Support Program for Outstanding Young Talents in Anhui Province Colleges and Universities(KJ2020A0526); Horizontal Cooperation Project of Fuyang Municipal Government(XDHX201722); Major Science and Technology Projects of Anhui Province(18030701213)

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摘要/Abstract

氧取代N-羟基邻苯二甲酰亚胺衍生物广泛存在于天然产物和药物中, 其合成具有重要的意义. 大多数烯烃、酮、酯、醛和醇的C=C/C—H键的活化方法通常需要用到金属或过氧化物. 以廉价安全的醋酸碘苯作为脱氢剂, N-羟基邻苯二甲酰亚胺为自由基前体, 实现了烯烃的双氧化、羰基α位氢的氧化、醛氢氧化及伯醇的氧化酯化反应. 该方法主要通过自由基机理, 具有环境友好、产率高及底物适用范围广等优点. 反应体系简单实用, 可以很好地应用于氧取代N-羟基邻苯二甲酰亚胺衍生物的合成.

关键词: 氧化交叉偶联, PINO (phthalimide nitrogen-oxygen)自由基, 非金属, 碘(III)

The synthesis of oxygen-substituted N-hydroxy phthalimide derivatives is essential due to their ubiquity in natural products and pharmaceuticals. Metals or peroxides are often required for most C=C/C—H bond activation methods used for olefins, ketones, esters, aldehydes and alcohols. Using cheap and safe iodobenzene diacetate as a feasible dehydrogenation agent and N-hydroxy phthalimide as free radical precursor, the dioxidation of olefins, α-oxidation of carbonyl compounds, oxidation of aldehydes, and oxidative esterification of primary alcohols were successfully realized. This method occurs via a radical mechanism and has the characteristics of mild metal-free reaction conditions, good compatibility and wide substrate scope.

Key words: oxidative cross-coupling, phthalimide nitrogen-oxygen radical, metal-free, iodine(III)

引用此文

吴福芳, 李雪健, 贾浩, 韩宣振, 沈晓宝. 碘(III)介导的碳自由基参与的氧化偶联反应[J]. 有机化学, 2022, 42(3): 884-890.

Fufang Wu, Xuejian Li, Hao Jia, Xuanzhen Han, Xiaobao Shen. Iodine(III)-Promoted Oxidative Cross-Coupling Reactions of C—H Bonds via a Free Radical Process[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 884-890.

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图/表 6

Scheme 1. Oxidative coupling using NHPI

Entry	Oxidant (equiv.)	Time/h	Yield^b/%
1	TBHP (2)	2	N.D.
2	H₂O₂ (2)	2	N.D.
3	PhI(OCOCF₃)₂ (2)	2	Trace
4	PhI(OAc)₂ (2)	2	85
5	PhI(OAc)₂ (2)	4	86
6	PhI(OAc)₂ (2)	6	83
7	PhI(OAc)₂ (2)	8	85
8	PhI(OAc)₂ (2)	12	82
9	PhI(OAc)₂ (0.1)	2	37
10	PhI(OAc)₂ (0.5)	2	53
11	PhI(OAc)₂ (1.0)	2	72
12	PhI(OAc)₂ (1.2)	2	86
13	PhI(OAc)₂ (1.5)	2	84

Table 1. Optimization of the reaction conditionsa

Scheme 2. Oxidation of different types of substrates with NHPI Reagents and conditions: NHPI (1 mmol), substrate (2 mmol), and PIDA (1.2 mmol) were added to DCM (2 mL) and the resulting reaction mixture was stirred at room temperature for 2 h. Isolated yield.

Scheme 3. Oxidative reaction of different alcohols with NHPI Reagents and conditions: NHPI (1 mmol), alcohol (2 mmol) and PIDA (1.2 mmol) were added to DCM (2 mL) and the resulting reaction mixture was stirred at room temperature for 2 h. Isolated yield.

Substrate	Product	Yield^c	Yield^d/%
Substrate	Product	Yield^c	TEMPO	BHT	DPPH
Methyl methacrylate	3	82	Trace	Trace	Trace
3-Methyl-2,4-pentanedione	8	89	15	14	Trace
4-Chlorobenzaldehyde	20	90	17	18	Trace
C₂H₅OH	13	86	Trace	Trace	Trace

Table 2. Gram-scale reaction and radical trapping experiment

Scheme 4. Proposed reaction mechanism

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碘(III)介导的碳自由基参与的氧化偶联反应

Iodine(III)-Promoted Oxidative Cross-Coupling Reactions of C—H Bonds via a Free Radical Process

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