A Widely Applicable Dual Catalytic System for Cross-Electrophile Coupling Enabled by Mechanistic Studies.
A Widely Applicable Dual Catalytic System for Cross-Electrophile Coupling Enabled by Mechanistic Studies.
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DOI：
10.1021/acscatal.0c03237
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发表时间：
2020-11-06
期刊：
影响因子：
12.9
通讯作者：
Zultanski SL
中科院分区：
文献类型：
--
作者：
Charboneau DJ;Barth EL;Hazari N;Uehling MR;Zultanski SL
描述了一种用于芳基卤化物和烷基卤化物之间的交叉亲电子偶联反应的双催化系统，该系统具有镍催化剂、钴助催化剂和温和的均相还原剂。机理研究表明，Ni催化剂活化芳基卤化物，而Co助催化剂活化烷基卤化物。这使得系统可以根据反应产物的分布，通过简单地修改镍和钴催化剂的负载量，针对各种底物类别进行合理优化。例如，使用相同的 Ni 和 Co 催化剂在相似的反应条件下演示了芳基溴和芳基碘与烷基溴、烷基碘和苄基氯的偶联，但在每种情况下具有不同的最佳催化剂负载量。我们的系统能够耐受多种官能团，并且能够偶联杂芳基卤化物、二邻位取代的芳基卤化物、药学相关的药物样芳基卤化物和各种烷基卤化物。此外，双催化平台促进了溴（碘）芳烃与两种不同的卤代烷的一系列选择性一锅三组分交叉亲电子偶联反应。这证明了该平台提供的独特控制水平，并能够快速生成分子复杂性。该系统可以很容易地用于广泛的应用，因为所有反应组分都是市售的，反应是可扩展的，并且不需要有毒的酰胺基溶剂。预计该策略以及潜在的机制框架将可推广到其他交叉亲电子偶联反应。
A dual catalytic system for cross-electrophile coupling reactions between aryl halides and alkyl halides that features a Ni catalyst, a Co cocatalyst, and a mild homogeneous reductant is described. Mechanistic studies indicate that the Ni catalyst activates the aryl halide, while the Co cocatalyst activates the alkyl halide. This allows the system to be rationally optimized for a variety of substrate classes by simply modifying the loadings of the Ni and Co catalysts based on the reaction product profile. For example, the coupling of aryl bromides and aryl iodides with alkyl bromides, alkyl iodides, and benzyl chlorides is demonstrated using the same Ni and Co catalysts under similar reaction conditions but with different optimal catalyst loadings in each case. Our system is tolerant of numerous functional groups and is capable of coupling heteroaryl halides, di-ortho-substituted aryl halides, pharmaceutically relevant druglike aryl halides, and a diverse range of alkyl halides. Additionally, the dual catalytic platform facilitates a series of selective one-pot three-component cross-electrophile coupling reactions of bromo(iodo)arenes with two distinct alkyl halides. This demonstrates the unique level of control that the platform provides and enables the rapid generation of molecular complexity. The system can be readily utilized for a wide range of applications as all reaction components are commercially available, the reaction is scalable, and toxic amide-based solvents are not required. It is anticipated that this strategy, as well as the underlying mechanistic framework, will be generalizable to other cross-electrophile coupling reactions.
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影响因子：
15
作者：
Biswas S;Weix DJ
通讯作者：
Weix DJ
影响因子：
16.6
作者：
Fyfe, James W. B.;Fazakerley, Neal J.;Watson, Allan J. B.
通讯作者：
Watson, Allan J. B.
影响因子：
15
作者：
Everson, Daniel A.;Jones, Brittany A.;Weix, Daniel J.
通讯作者：
Weix, Daniel J.
影响因子：
15
作者：
Diccianni, Justin B.;Katigbak, Joseph;Diao, Tianning
通讯作者：
Diao, Tianning
DOI：
10.1021/jo500507s
发表时间：
2014-06-06
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Everson DA;Weix DJ
通讯作者：
Weix DJ