Activation of C-O and C-N Bonds Using Non-Precious-Metal Catalysis.
Activation of C-O and C-N Bonds Using Non-Precious-Metal Catalysis.
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DOI：
10.1021/acscatal.0c03334
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发表时间：
2020-10-16
期刊：
影响因子：
12.9
通讯作者：
Garg NK
中科院分区：
文献类型：
--
作者：
Boit TB;Bulger AS;Dander JE;Garg NK
金属催化的交叉偶联代表了现代合成化学中最重要的反应平台之一（图1A）。[1]尽管交叉偶联化学有着悠久的历史，但人们对拓展交叉偶联化学的前沿领域仍有浓厚的兴趣。目前探索的一些领域包括开发新的反应模式（双催化，2光氧化还原催化，3交叉亲电偶联，4化学酶转化，5等），立体选择性偶联，6和利用新类别的亲电试剂。相对于贵金属替代品，非贵金属催化剂除了潜在的成本、毒性和环境效益之外，还可以实现独特且具有挑战性的转化（图1A）。[7]特别是铁催化剂7a、f、j和镍催化剂7 f-j已成为该竞技场的焦点。在我们的实验室于2007年开始时，镍催化的交叉偶联是已知的，但与钯催化的变体相比，研究明显不足。自2007年以来，已经发表了1200多篇涉及镍催化交联的手稿。8此外，在过去十年中发表了几篇关于镍催化进展的评论，突出了这一领域的迅速发展。[7]这种扩张在很大程度上是由于认识到镍参与单电子过程9和激活强键10的能力，而强键10在历史上被认为在交叉偶联反应中是惰性的。7 e，11值得注意的是，在交叉偶联中使用非传统结构单元（例如苯胺、苯酚和羧酸衍生物）具有几个优点，因为它们的丰度、工作台稳定性、作为导向基团的实用性以及与更常见的芳基和酰卤亲电试剂的正交反应性（图1 B）。因此，这些方法可以实现新的断开和合成策略的改进。在强键活化的背景下，12我们的实验室一直对使用镍或铁催化的苯酚、酰胺和酯亲电体的活化和交叉偶联特别感兴趣。在此，我们强调了我们实验室在这一领域的贡献，如图2所示。首先，我们考虑苯酚衍生的新戊酸酯、碳酸酯、氨基甲酸酯和氨基磺酸酯的交叉偶联，以形成C-N和C-C键（图2A）。此外，我们讨论了我们的努力，以开发镍催化活化的酯和酰胺（图2 B和2 C，分别）。在说明性的地方，我们还概述了一些
Metal-catalyzed cross-couplings represent one of the most important reaction platforms in modern synthetic chemistry (Figure 1 A). 1 Although the field enjoys a rich history, there remains fervent interest in expanding the frontiers of crosscoupling chemistry. Some areas of current exploration include the development of new modes of reactivity (dual catalysis, 2 photoredox catalysis, 3 cross-electrophile couplings, 4 chemoenzymatic transformations, 5 etc.), stereoselective couplings, 6 and the utilization of new classes of electrophiles. With respect to the latter, non-precious-metal catalysis has been particularly enabling.In addition to potential cost, toxicity, and environmental benefits relative to precious-metal alternatives, non-preciousmetal catalysts can effect unique and challenging transformations (Figure 1 A). 7 In particular, iron catalysis 7a, f, j and nickel catalysis 7f− j have become focal points in this arena. At the time our laboratory began in 2007, nickel-catalyzed crosscouplings were known but significantly underexplored, compared to palladium-catalyzed variants. Since 2007, more than 1200 manuscripts involving nickel-catalyzed crosscouplings have been published. 8 Moreover, several reviews covering advances in nickel catalysis have been published over the past decade, highlighting the rapid growth of the field. 7 This expansion has largely been driven by recognition of nickel’s ability to participate in single-electron processes 9 and to activate strong bonds 10 historically considered inert in cross-coupling reactions. 7e, 11 Notably, the use of nontraditional building blocks (eg, aniline, phenol, and carboxylic acid derivatives) in crosscouplings offers several advantages, because of their abundance, bench stability, utility as directing groups, and orthogonal reactivity to more common aryl and acyl halide electrophiles (Figure 1 B). As a result, these methodologies can enable novel disconnections and improvements in synthetic strategy. In the context of strong bond activation, 12 our laboratory has been particularly interested in the activation and cross-coupling of phenol, amide, and ester electrophiles, using nickel or iron catalysis. Herein, we highlight our laboratory’s contributions in this area, which are summarized in Figure 2. First, we consider cross-couplings of phenol-derived pivalates, carbonates, carbamates, and sulfamates to form C− N and C− C bonds (Figure 2 A). In addition, we discuss our efforts to develop nickelcatalyzed activations of esters and amides (Figures 2 B and 2 C, respectively). Where illustrative, we also outline some of the
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影响因子：
15
作者：
Brozek, Laura A.;Ardolino, Michael J.;Morken, James P.
通讯作者：
Morken, James P.
影响因子：
5.2
作者：
Amani J;Alam R;Badir S;Molander GA
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Molander GA
影响因子：
16.6
作者：
Ben Halima, Taoufik;Masson-Makdissi, Jeanne;Newman, Stephen G.
通讯作者：
Newman, Stephen G.
影响因子：
15
作者：
Bercot, EA;Rovis, T
通讯作者：
Rovis, T
影响因子：
7.3
作者：
Brow, Dean G.;Bostrom, Jonas
通讯作者：
Bostrom, Jonas