四丁基三溴化铵促进的有机硼酸在无过渡金属条件下的脱硼硒化、溴化和羟基化反应

doi:10.6023/cjoc202312023

摘要/Abstract

介绍了无过渡金属下四丁基三溴化铵(TBATB)促进的有机硼酸的原位多功能化的简易方法. 通过这些方法, 各种有机硼能够以中等至优异的收率转化为相应的硒化、溴化或羟基化产物. 该反应具有条件温和、无过渡金属、底物适用范围广泛、操作简单等优点, 为有机硼的原位功能化提供了有前途的思路.

关键词: 四丁基三溴化铵, 有机硼酸, 硒化, 溴化, 羟基化, 无过渡金属

Divergent approaches for the convenient ipso-functionalization of organic boronic acids are presented, capitalizing on tetrabutylammonium tribromide (TBATB) under different, yet transition metal-free conditions. Through these methods, a wide array of organoborons can be efficiently converted into their corresponding selenylated, brominated, or hydroxylated products in moderate to excellent yields. The versatility of this strategy lies in its transition metal-free conditions, simple operation, and step-economic pathways, offering a promising idea for the ipso-functionalization of organoborons

Key words: tetrabutylammonium tribromide, organic boronic acid, selenylation, bromination, hydroxylation, transition metal-free

引用此文

田永盛, 魏斓枫, 黄嘉为, 韦玉, 徐亮, 刘帅. 四丁基三溴化铵促进的有机硼酸在无过渡金属条件下的脱硼硒化、溴化和羟基化反应[J]. 有机化学, 2024, 44(6): 1987-1997.

Yongsheng Tian, Lanfeng Wei, Jiawei Huang, Yu Wei, Liang Xu, Shuai Liu. Deboronative Selenylation, Bromination, or Hydroxylation of Organic Boronic Acids Facilitated by Tetrabutylammonium Tribromide under Transition Metal-Free Conditions[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1987-1997.

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图/表 7

图1. 有机硼化合物的转化

Scheme 1. Conversion of organoborate compound

Entry	Variation from the standard conditions	Yield^b/%
1	None	92
2	Without TBATB	N.R.^c
3	TBATB (10 mol%)	65
4	Without light (in dark)	90
5	Without O₂ (with Ar)	87
6	DMF instead of DMSO	31
7	MeCN instead of DMSO	17
8	MeOH instead of DMSO	29
9	Room temperature	47
10	80 ℃ instead of 100 ℃	79
11	90 ℃ instead of 100 ℃	85
12	10 h instead of 12 h	86
13	11 h instead of 12 h	90

表1. 硼酸脱硼硒基化反应条件优化a

Table 1. Optimization of the reaction condition for organoboric acid deboronative selenylation

表2. 脱硼硒化的底物范围a,b

Table 2. Substrate scope of deboronative selenylation

表3. 脱硼溴化的底物范围a,b

Table 3. Substrate scope of deboronative bromination

表4. 脱硼羟基化的底物范围a,b

Table 4. Substrate scope of deboronative hydroxylation

图2. 苯硼酸频哪醇酯脱硼硒基化反应、克级反应和机理验证实验

Scheme 2. Phenylboronic acid pinacol ester deboronative selenylation reaction, gram-scale reaction and mechanism experiments

图3. 芳基硼酸脱硼硒基化反应可能的反应机理

Scheme 3. Proposed mechanism of arylboronic acid deboronative selenylation reaction

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