无金属条件下亚磺酸钠与酚类化合物形成芳基磺酸酯的电化学合成反应

doi:10.6023/cjoc202107060

摘要/Abstract

通过电化学氧化方法, 实现了酚与亚磺酸钠类化合物中等到高收率的磺酰化反应, 获得了具有良好官能团耐受性的芳基磺酰酯. 杀螨酯的合成和克级反应的实施, 验证了该绿色方案的实用性. 循环伏安实验表明, 标准条件下亚磺酸盐的氧化先于酚的氧化, 且该过程涉及自由基.

关键词: 电化学合成, 芳基磺酸酯, 无金属条件, 绿色方法

An electrochemical oxidative sulfonylation of phenols with sodium sulfinates has been established to produce arylsulfonyl esters with good functional group tolerance in moderate to high yields. The synthesis of chlorfenson and a gram-scale reaction have been performed to evaluate the practicality of this green protocol. Cyclic voltammetry experiments indicate that the oxidation of sulfinate occurs prior to that of phenol substrate under standard conditions, and free radical is involved in the process.

Key words: electrochemical synthesis, aryl sulfonates, metal-free conditions, green method

引用此文

付拯江, 杨振江, 孙丽, 尹健, 伊学政, 蔡琥, 雷爱文. 无金属条件下亚磺酸钠与酚类化合物形成芳基磺酸酯的电化学合成反应[J]. 有机化学, 2022, 42(2): 600-606.

Zhengjiang Fu, Zhenjiang Yang, Li Sun, Jian Yin, Xuezheng Yi, Hu Cai, Aiwen Lei. Electrochemical Synthesis of Aryl Sulfonates from Sodium Sulfinates and Phenols under Metal-Free Conditions[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 600-606.

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图/表 8

Entry	Variation from the standard conditions	Yield^b/%
1	None	95 (90)^c
2	No water	25
3	No 15-crown-5	39
4	CH₃CN instead of DMF	49
5	13 mA instead of 11 mA	76
6	10 mA and 3.3 h instead of 11 mA and 3 h	85
7	Pt(+) instead of C(+)	82
8	Ni(–) instead of Pt(–)	60
9	No electricity	0

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope of phenols with isolated yieldsa

Table 3. Substrate scope of phenols with isolated yieldsa

Scheme 1. Electrochemical oxidative sulfonylation of alcohols

Scheme 2. Synthesis of chlorfenson (3gf) and gram scale synthesis of phenyl benzenesulfonate (3aa)

Figure 1. Cyclic voltammograms of substrate 1a, 2a

Scheme 3. Radical-trapping experiment

Scheme 4. Proposed mechanism

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