Metal‐Free, Multicomponent Anti‐Markovnikov Hydroarylsulfonylation and Alkoxyarylsulfonylation of Vinyl Arenes,Advanced Synthesis & Catalysis

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Metal‐Free, Multicomponent Anti‐Markovnikov Hydroarylsulfonylation and Alkoxyarylsulfonylation of Vinyl Arenes
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2020-11-25 , DOI: 10.1002/adsc.202000995
Pritha Das ₁ , Subhodeep Das ₁ , Kasarla Varalaxmi _{1,

2} , Ranjan Jana _{1,

3}

Affiliation

A unified strategy for the hydro‐arylsulfonylation of vinyl arenes has been developed under catalyst, additive‐free conditions at room temperature from the corresponding aryldiazonium salts, DABSO (DABCO ⋅ 2SO₂), and thiophenol as hydrogen atom transfer (HAT) reagent. Mechanistically, an incipient arylsulfonyl radical is generated from the corresponding aryl diazonium salts and DABSO which undergoes anti‐Markovnikov addition to styrenes followed by hydrogen atom transfer from thiophenol. Interestingly, this multi‐component reaction is highly chemoselective suppressing deleterious thiosulfonylation and thiol‐ene reactions. Tuning the reaction conditions, a four‐component difunctionalization with alkoxy group has been achieved using 1,4‐dicyanobenzene as an oxidant. Furthermore, base‐promoted elimination to form vinyl sulfone has been also examined. The practicability of this present reaction has been demonstrated by the ex situ generation of sulfur dioxide in an H‐type reaction vessel and subsequent hydro‐ and alkoxyarylsulfonylation in good to moderate yields. The hydroarylsulfonylation reaction is scalable and applied to a metal‐free synthesis of the key intermediate for an anti‐migraine drug Eletriptan.

中文翻译：

乙烯基芳烃的无金属，多组分抗马尔科夫尼科夫加氢芳基磺酰化和烷氧基芳基磺酰化

在室温下，在催化剂，无添加剂条件下，由相应的芳基重氮盐DABSO（DABCO⋅2SO _2）开发了统一的乙烯基芳烃磺酰基磺化策略。）和硫酚作为氢原子转移（HAT）试剂。从机理上讲，相应的芳基重氮盐和DABSO会生成一个初始的芳基磺酰基基团，对苯乙烯进行抗马氏化学加成，然后从硫酚中转移氢原子。有趣的是，这种多组分反应具有高度的化学选择性，可抑制有害的硫磺酰化反应和硫醇烯反应。通过调节反应条件，使用1,4-二氰基苯作为氧化剂已实现了带有烷氧基的四组分双官能化。此外，还研究了碱促进的消除反应以形成乙烯基砜。这种本反应的实用性已通过异位证明。在H型反应容器中生成二氧化硫，并随后以良好至中等的收率进行加氢和烷氧基芳基磺酰化反应。加氢芳基磺酰化反应具有可扩展性，可用于抗偏头痛药物依曲普坦的关键中间体的无金属合成。

更新日期：2021-01-19

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