缺电子芳香环的选择性烷基化:可见光光氧化还原催化[1.1.1]丙烷的自由基双官能化

IF 4.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Chengjun Chen , Xiaoyu Shen , Shengkun Guo , Ruizhe Yan , Huaguang Yu , Ying Han , Qiu Sun , Shaoqun Zhu
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引用次数: 0

摘要

我们在此报道了一种可见光光氧化还原催化的[1.1.1]丙烷与缺电子芳香环和Katritzky盐的三组分自由基偶联,以良好的分离产率获得结构多样的芳基化双环[1.1.1]戊烷。利用缺乏电子的芳基环作为芳基源,对叔BCP碳自由基的选择性芳基化至关重要。通过大规模反应和产物的合成衍生化,证明了本方案的合成效用。苯环广泛存在于约45%的fda批准的药物中。然而,苯环部分的非战略性结合通常会导致候选分子[1]的物理化学特征受到损害。因此,使用电子同位异构体,如双环[1.1.1]戊烷(BCP)来取代苯环成为有效解决这些限制的一种有希望的策略,以及几种基于BCP的候选药物,包括BCP- mglur1拮抗剂,BCP-他zarotene,bcp -白藜芦醇在抗抑郁治疗、肝性脑病治疗、牛皮癣治疗和心血管保护等不同领域具有显著的治疗潜力,在过去的十年中得到了发展(方案1a)。[2-5]目前芳基化BCP衍生物的合成主要依赖于C-C键偶联策略,这往往受到步骤经济性差、反应条件苛刻和底物范围有限的限制。[6-9]因此,开发有效的芳基化BCP合成方法仍然是合成化学领域的一项挑战性任务。Gutierrez,[10] Molander,[11]和Xu[12]最近的进展证明了通过[1.1.1]丙烷,芳香族杂环和各种自由基前体,包括三氟硼酸盐[13]和卤代烷(方案1b)的反应合成BCP的可行性尽管取得了重大进展,但烷基自由基在芳烃上的位置选择性安装仍然是一个挑战。利用过渡金属作为催化剂进行交叉偶联反应是最直接的方法之一,但通常采用芳基格氏试剂和卤化芳烃等活化的芳香族基团。基于Minisci反应的杂环芳烃自由基芳基化是另一种有效的方法,但必须使用含氮杂环,且总是得到c2选择性烷基化产物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Site-selective alkylation of electron-deficient aromatic cycles: visible-light photoredox-catalyzed radical di-functionalization of [1.1.1]propellane†
We report herein a visible-light photoredox-catalyzed three-component radical coupling of [1.1.1]propellane with electron-deficient aromatic cycles and Katritzky salts, accessing structurally diverse alkyl arylated bicyclo[1.1.1]pentanes in good isolated yields. The use of electron-deficient aromatic cycles as an aryl source was crucial for the site-selective arylation of tertiary BCP carbon radicals. The synthetic utility of the present protocol was demonstrated by a large-scale reaction and synthetic derivatization of the product.
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来源期刊
Chemical Communications
Chemical Communications 化学-化学综合
CiteScore
8.60
自引率
4.10%
发文量
2705
审稿时长
1.4 months
期刊介绍: ChemComm (Chemical Communications) is renowned as the fastest publisher of articles providing information on new avenues of research, drawn from all the world''s major areas of chemical research.
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