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

doi:10.6023/cjoc202109012

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (3): 884-890.DOI: 10.6023/cjoc202109012 Previous Articles Next Articles

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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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Abstract

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)

Cite this article

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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Fig. & Tab. 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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