Main Group Catalyzed Arene Borylation: Challenges and Opportunities.
Main Group Catalyzed Arene Borylation: Challenges and Opportunities.
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DOI：
10.1021/acscatal.3c01668
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发表时间：
2023-06-02
期刊：
影响因子：
12.9
通讯作者：
Ingleson, Michael J. J.
中科院分区：
文献类型：
--
作者：
Ingleson, Michael J. J.
C-H硼基化是一种有效的方法，可以生成有机硼烷，这在很大程度上是由于Suzuki-Miyaura反应。[1]使用基于过渡金属的催化剂进行芳烃C-H硼基化反应已经取得了巨大的进展。2这些催化剂通常利用过渡金属的可变氧化态来实现C-H裂解和B键的形成。特别是铱基C-H硼基化催化剂被确立为C-H官能化领域中最重要的方法之一。3主族化合物也被用作芳烃C-H硼基化反应的催化剂，相对于贵金属，大多数主族元素的丰度更高，成本更低，允许接触限值更高，这是这项研究的关键驱动力。4第二个驱动因素源于这样的事实，即主基催化通常在固定的氧化态下进行，因此需要不同的硼化机制。这可以导致与使用基于过渡金属的催化剂互补的区域选择性和官能团耐受性。然而，在主基催化的芳烃硼基化中仍然存在重大挑战，特别是围绕扩大底物范围和产生操作简单的方法。5迄今为止报道的大多数系统使用的（预）催化剂难以处理（由于它们对质子物质如H2O的敏感性），并且在底物范围上限于亲核（杂）芳烃（本文定义为Mayr亲核性值（N）> 1的底物，作为参考，2-Me-噻吩和呋喃具有N ≥ 1.3）。6确定一个单一的催化体系，解决这两个挑战是必不可少的主基催化芳烃C-H硼基化的更广泛的吸收。这一观点总结了迄今为止在主基催化的分子间芳烃C-H硼基化反应中使用的一般方法。它不是对该领域的全面调查;相反，它侧重于分析共同的关键步骤，并通过这一点来强调该领域目前的一些挑战和未来的机会。对于化学计量（在强刘易斯酸中）7和分子内C− H硼基化，读者可以参考最近的综述。8
C− H borylation is an efficient method to generate organoboranes that are powerful intermediates in synthesis, due in large part to the Suzuki− Miyaura reaction. 1 Tremendous advances have been made using transition metal based catalysts for arene C− H borylation. 2 These catalysts generally utilize the variable oxidation states available to the transition metals to effect C− H cleavage and C− B bond formation. Iridium based C− H borylation catalysts in particular are established as one of the foremost methods in the field of C− H functionalization. 3 Main group compounds also have been applied as catalysts for arene C− H borylation, with the greater abundance, lower cost, and higher permitted exposure limits of most main group elements relative to precious metals one key driver for this research. 4 A second driver stems from the fact that main group catalysis generally proceeds at a fixed oxidation state thus requiring distinct borylation mechanisms. This can lead to complementary regioselectivity and functional group tolerance to that using transition metal based catalysts. However, significant challenges remain in main group catalyzed arene borylation, particularly around expanding the substrate scope and generating operationally simple methodologies. 5 Most systems reported to date use (pre) catalysts that are challenging to handle (due to their sensitivity to protic species such as H2O) and that are limited in substrate scope to nucleophilic (hetero) arenes (defined herein as substrates with Mayr nucleophilicity values (N)> 1, for reference, 2-Me-thiophene and furan have N≈ 1.3). 6 Identifying a single catalytic system that addresses both of these challenges is essential for the wider uptake of main group catalyzed arene C− H borylation. This viewpoint summarizes the general approaches used to date in main group catalyzed intermolecular arene C− H borylation. It is not a comprehensive survey of the area; instead, it focuses on analyzing common key steps and through this seeks to highlight some of the current challenges and future opportunities in the field. For stoichiometric (in strong Lewis acid) 7 and intramolecular C− H borylation, the reader is directed to recent reviews. 8
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影响因子：
8.4
作者：
Grundy ME;Yuan K;Nichol GS;Ingleson MJ
通讯作者：
Ingleson MJ
影响因子：
1.4
作者：
Desrosiers, Vincent;Gaudy, Audrey;Fontaine, Frederic-Georges
通讯作者：
Fontaine, Frederic-Georges
影响因子：
3.4
作者：
Jayaraman, Arumugam;Castro, Luis C. Misal;Fontaine, Frederic-Georges
通讯作者：
Fontaine, Frederic-Georges
影响因子：
2.8
作者：
Del Grosso, Alessandro;Pritchard, Robin G.;Ingleson, Michael J.
通讯作者：
Ingleson, Michael J.
影响因子：
4.3
作者：
Liu, Yun-Lin;Kehr, Gerald;Erker, Gerhard
通讯作者：
Erker, Gerhard