4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

doi:10.6023/cjoc202103041

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (5): 1957-1967.DOI: 10.6023/cjoc202103041 Previous Articles Next Articles

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4-二甲胺基吡啶-硼自由基促进的缺电子烯烃区域选择性硼氢化反应

黄云帅¹, 靳小慧¹, 张凤莲¹^,^*(), 汪义丰¹^,^*()

1 中国科学技术大学化学系合肥 230026

收稿日期:2021-03-23 修回日期:2021-04-09 发布日期:2021-04-25
通讯作者: 张凤莲, 汪义丰
基金资助:
国家自然科学基金(21971226); 中央高校基本科研业务费专项资金(WK2060000017)

4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

Yunshuai Huang¹, Xiaohui Jin¹, Fenglian Zhang¹^,^*(), Yifeng Wang¹^,^*()

1 Department of Chemistry, University of Science and Technology of China, Hefei 230026

Received:2021-03-23 Revised:2021-04-09 Published:2021-04-25
Contact: Fenglian Zhang, Yifeng Wang
About author:
* Corresponding authors. E-mail: zfl9@ustc.edu.cn;
E-mail: yfwangzj@ustc.edu.cn
Supported by:
National Natural Science Foundation of China(21971226); Fundamental Research Funds for the Central Universities(WK2060000017)

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Abstract

Organoboron compounds have shown significant applications in modern chemical synthesis. Hydroboration of alkenes is among the most widely used methods to access these targets. Herein, a regioselective radical hydroboration reaction of electron-deficient alkenes with 4-dimethylaminopyridine (DMAP)-boryl radical for the synthesis of α-boryl functionalized molecules is reported. The reaction features specific α-regioselectivity, mild reaction conditions, good functional group tolerance, and broad substrate scope. α,β-Unsaturated esters, amides, carboxylic acid, nitrile, trifluoromethyl molecule, sulfone, and phosphonate are viable substrates for this reaction. The resulting α-boryl functionalized molecules can be further transformed to various useful building blocks.

Key words: 4-dimethylaminopyridine-boryl radical, electron-deficient alkenes, regioselectivity, hydroboration, radical chemistry

Cite this article

Yunshuai Huang, Xiaohui Jin, Fenglian Zhang, Yifeng Wang. 4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 1957-1967.

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Entry	PhSH (x mol%)	Initiator	Conditions	Yield^b/% of 3aa
1	50	AIBN	80 ℃, 9 h	46
2	50	ACCN	95 ℃, 9 h	55
3	50	ABVN	60 ℃, 4 h	69
4	50	TBHN	60 ℃, 4 h	83
5	50	Et₃B	Air, r.t., 9 h	85^c
6	20	Et₃B	Air, r.t., 9 h	84^c
7	20	—	O₂, r.t., 9 h	0 (>95)^d
8^e	20	Et₃B	Air, r.t., 9 h	0 (>95)^d

Entry	PhSH (x mol%)	Initiator	Conditions	Yield^b/% of 3aa
1	50	AIBN	80 ℃, 9 h	46
2	50	ACCN	95 ℃, 9 h	55
3	50	ABVN	60 ℃, 4 h	69
4	50	TBHN	60 ℃, 4 h	83
5	50	Et₃B	Air, r.t., 9 h	85^c
6	20	Et₃B	Air, r.t., 9 h	84^c
7	20	—	O₂, r.t., 9 h	0 (>95)^d
8^e	20	Et₃B	Air, r.t., 9 h	0 (>95)^d

4-二甲胺基吡啶-硼自由基促进的缺电子烯烃区域选择性硼氢化反应

4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

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