Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions.
Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions.
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叶立德取代的膦：用于金催化和钯催化偶联反应的强供体配体平台。
DOI：
10.1021/acs.accounts.1c00797
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发表时间：
2022
影响因子：
18.3
通讯作者：
V. H. Gessner
中科院分区：
文献类型：
--
作者：
S. Lapointe;Abir Sarbajna;V. H. Gessner
结论：均相催化剂的发展与新的、复杂的配体的设计密切相关，这些配体通过操纵金属的电子性质及其空间环境来解决给定反应方案的局限性。膦配体是一类特殊的配体，在许多催化转化中有应用，从氢化反应到加氢反应和偶联化学。多年来，化学家们一直在努力提高偶联反应的效率、选择性和应用。使用高富电子和大体积的膦通常与增加的选择性和效率相关，并导致开发了大量的富电子烷基取代的膦。然而，这种增加配体给体强度的概念在使用三烷基取代的膦时达到其极限，其中三叔丁基膦因此多年来是最具活性的配体之一。在利用叶立德特殊的给体强度稳定缺电子低价主族化合物的研究过程中，我们发现叶立德取代的膦（YPhos）配体具有非常强的给体能力。此外，YPhos配体通过改变磷、膦或中心叶立德碳原子上的基团的性质是高度可调的。因此，我们得到了一个配体平台，其给体能力从PCy 3到比N-杂环卡宾更强的给体能力，同时比简单的膦以及许多众所周知的联芳基膦配体更需要空间。在最近的一系列报告中，我们的团队将YPhos配体应用于金和钯催化的反应中，其催化负载量适用于中到大规模的应用。增加的供体强度和独特的结构允许在温和的反应条件下在一系列转化中具有显着的活性。对于金（I）催化的反应，我们得到的周转数（吨）的苯乙炔与苯胺的氢胺化超过20 000。此外，更复杂的反应容易催化，效率高于其他已知的金（I）催化剂。在一系列钯催化的偶联反应中也发现了类似的效果。在Buchwald-Hartwig胺化反应中，芳基氯的胺化反应在室温下达到了前所未有的活性。催化活性单-YPhos钯物质的形成速度允许一些胺化反应仅在几分钟内完成。配体设计的调整使得能够使用各种不同的空间位阻需求的不同芳基和烷基胺。此外，YPhos配体一般在各种碳亲核试剂与芳基氯、溴和三氟甲磺酸酯的偶联中显示出高活性和选择性。这使得能够开发用于无阻碍酮的α-芳基化和格氏试剂与锌试剂的偶联以及氯代芳烃与烷基锂化合物的首次有效偶联的有效反应方案。综述了近年来YPhos配体的研究进展及其在金、钯催化中的应用。我们也希望在未来刺激这种配体平台在催化中的进一步使用。
ConspectusThe development of homogeneous catalysts is strongly connected to the design of new, sophisticated ligands, which resolve limitations of a given reaction protocol by manipulating the electronic properties of the metal and its spatial environment. Phosphines are a privileged class of ligands that find applications in many catalytic transformations, ranging from hydrogenation reactions to hydroformylation and coupling chemistry. For many years, chemists have been trying to improve the efficiency, selectivity, and application of coupling reactions. The use of highly electron-rich and bulky phosphines was often associated with increased selectivity and efficiency and led to the development of a vast variety of electron-rich alkyl-substituted phosphines. However, this concept of increasing the ligand donor strength reaches its limits with the use of trialkyl-substituted phosphines with tri-tert-butylphosphine thus being one of the most active ligands for many years. In the course of our research efforts to use the special donor strength of ylides to stabilize electron-deficient, low-valent main group compounds, we realized that ylide-substituted phosphine (YPhos) ligands possess remarkably strong donor abilities. Moreover, the YPhos ligands are highly tunable by changing the nature of the groups on the phosphonium, phosphine, or central ylidic carbon atom. We thus obtained a ligand platform with donor capabilities ranging from PCy3 to even stronger donor abilities than N-heterocyclic carbenes, while being more sterically demanding than simple phosphines as well as many well-known biarylphosphine ligands.These properties led us to explore the applicability of the YPhos ligands in catalysis. In a series of recent reports, our group applied YPhos ligands in gold and palladium catalyzed reactions at catalytic loadings applicable for medium- to large-scale applications. The increased donor strength and unique architecture allowed for remarkable activities in a series of transformations at mild reactions conditions. For gold(I)-catalyzed reactions, we obtained turnover numbers (TONs) for the hydroamination of phenylacetylene with aniline of over 20 000. Also, more complex reactions were easily catalyzed with efficiencies greater than those of other known gold(I) catalysts. Similar efficacies were found in a series of palladium-catalyzed coupling reactions. In Buchwald-Hartwig aminations, unprecedented activities for the amination of aryl chlorides were reached at room temperature. The speed of formation of the catalytically active mono-YPhos palladium species allowed for some of the amination reactions to be completed in only a few minutes. Adjustment of the ligand design enabled the use of a large variety of different aryl and alkyl amines of different steric demands. Furthermore, the YPhos ligands in general showed high activities and selectivity in the coupling of a variety of carbon nucleophiles with aryl chlorides, bromides, and triflates. This enabled the development of efficient reaction protocols for the α-arylation of unhindered ketones and the coupling of Grignard and zinc reagents as well as the first efficient coupling of chloroarenes with alkyllithium compounds. This Account summarizes the recent development of YPhos ligands and their application in gold and palladium catalysis. We also hope to stimulate further use of this ligand platform in catalysis in the future.
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影响因子：
18.3
作者：
Martin, Ruben;Buchwald, Stephen L.
通讯作者：
Buchwald, Stephen L.
快速激活铃木 - 米龙和芳基酯的布赫瓦尔德 - 哈特维格耦合的PD-催化剂。
DOI：
10.1021/acs.joc.7b02588
发表时间：
2018-01-05
期刊：
The Journal of organic chemistry
影响因子：
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作者：
Dardir AH;Melvin PR;Davis RM;Hazari N;Mohadjer Beromi M
通讯作者：
Mohadjer Beromi M
DOI：
10.1021/jo401476f
发表时间：
2013-09-06
期刊：
The Journal of organic chemistry
影响因子：
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作者：
Hama T;Ge S;Hartwig JF
通讯作者：
Hartwig JF
影响因子：
15.7
作者：
Huang B;Hu M;Toste FD
通讯作者：
Toste FD
弥合 Bisylides 和 Methandiides 之间的差距：Yldiide 的分离、反应性和电子结构
影响因子：
--
作者：
T. Scherpf;R. Wirth;S. Molitor;K.-S. Feichtner;V. H. Gessner
通讯作者：
V. H. Gessner