Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands.
Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands.
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DOI：
10.1021/ar800036s
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发表时间：
2008-11-18
影响因子：
18.3
通讯作者：
Buchwald, Stephen L.
中科院分区：
文献类型：
--
作者：
Martin, Ruben;Buchwald, Stephen L.
许多类型的聚合物、配体、天然产物和药物的核心都含有联芳基或取代的芳香结构，而合成这些结构的有效方法对于广大有机化学家的工作至关重要。最近，钯催化的碳 - 碳键形成过程，特别是铃木 - 宫浦交叉偶联反应（SMC），为此目的而受到广泛关注。与构建这些部分的其他方法相比，SMC具有许多优势，包括反应条件温和、对官能团的耐受性高、试剂的商业可得性和稳定性，以及从反应混合物中处理和分离副产物的简便性。
直到1998年，大多数用于SMC的催化剂都使用三芳基膦配体。最近，新的大体积且富电子的膦配体被引入，它们可以显著提高此类交叉偶联反应的效率和选择性。在我们对碳 - 氮键形成反应的研究过程中，我们发现使用富电子且大体积的膦配体提高了氧化加成和还原消除过程的速率；这是我们开发一类新配体——二烷基联芳基膦L1 - L12的开端。这些配体可用于多种钯催化的碳 - 碳、碳 - 氮和碳 - 氧键形成过程，并且还可作为许多其他反应的辅助配体。
这些催化剂增强的反应活性扩大了可用于SMC的交叉偶联伙伴的范围。使用这种二烷基联芳基膦配体，未活化的芳基氯、芳基对甲苯磺酸酯、杂芳基体系以及受阻严重的底物组合的偶联已成为常规操作。这些配体的实用性已在众多合成应用中成功得到证明，包括与工业相关的过程。
在本文中，我们概述了二烷基联芳基膦配体在SMC中的使用及其影响。我们讨论了我们对反应机理框架的研究，这使我们能够合理地修饰配体结构以调整其性能。我们还描述了在天然产物和新材料合成中的一些选定应用，以说明这些二烷基联芳基膦配体在各种“实际”合成应用中的实用性。
The cores of many types of polymers, ligands, natural products, and pharmaceuticals contain biaryl or substituted aromatic structures, and efficient methods of synthesizing these structures are crucial to the work of a broad spectrum of organic chemists. Recently, Pd-catalyzed carbon-carbon bond-forming processes, particularly the Suzuki–Miyaura cross-coupling reaction (SMC), have risen in popularity for this purpose. The SMC has many advantages over other methods for constructing these moieties, including mild conditions, high tolerance toward functional groups, the commercial availability and stability of its reagents, and the ease of handling and separating byproducts from its reaction mixtures. Until 1998, most catalysts for the SMC employed triarylphosphine ligands. More recently, new bulky and electron-rich phosphine ligands, which can dramatically improve the efficiency and selectivity of such cross-coupling reactions, have been introduced. In the course of our studies on carbon-nitrogen bond-forming reactions, we found that the use of electron-rich and bulky phosphines enhanced the rate of both the oxidative addition and reductive elimination processes; this was the beginning of our development of a new family of ligands, the dialkylbiarylphosphines L1–L12. These ligands can be used for a wide variety of palladium-catalyzed carbon–carbon, carbon–nitrogen, and carbon–oxygen bond-forming processes as well as serving as supporting ligands for a number of other reactions. The enhanced reactivity of these catalysts has expanded the scope of cross-coupling partners that can be employed in the SMC. Using such dialkylbiarylphosphine ligands, the coupling of unactivated aryl chlorides, aryl tosylates, heteroaryl systems, and very hindered substrate combinations have become routine. The utility of these ligands has been successfully demonstrated in a wide number of synthetic applications, including industrially relevant processes. In this account, we provide an overview of the use and impact of dialkylbiarylphosphine ligands in the SMC. We discuss our studies on the mechanistic framework of the reaction, which have allowed us to rationally modify the ligand structures in order to tune their properties. We also describe selected applications in the synthesis of natural products and new materials to illustrate the utility of these dialkylbiarylphosphine ligands in various “real-world” synthetic applications.
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影响因子：
3.6
作者：
Cattoen, Xavier;Pericas, Miquel A.
通讯作者：
Pericas, Miquel A.
影响因子：
3.4
作者：
Caron, S;Massett, SS;Braish, TF
通讯作者：
Braish, TF
影响因子：
2.3
作者：
Braga, Ataualpa A. C.;Morgon, Nelson H.;Maseras, Feliu
通讯作者：
Maseras, Feliu
影响因子：
15
作者：
Barder, Timothy E.;Buchwald, Stephen L.
通讯作者：
Buchwald, Stephen L.
影响因子：
15
作者：
Braga, AAC;Morgon, NH;Maseras, F
通讯作者：
Maseras, F