The Road Less Traveled: Unconventional Site Selectivity in Palladium-Catalyzed Cross-Couplings of Dihalogenated N-Heteroarenes.
The Road Less Traveled: Unconventional Site Selectivity in Palladium-Catalyzed Cross-Couplings of Dihalogenated N-Heteroarenes.
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DOI：
10.1021/acscatal.2c03743
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发表时间：
2022-10-07
期刊：
影响因子：
12.9
通讯作者：
Neufeldt SR
中科院分区：
文献类型：
--
作者：
Norman JP;Neufeldt SR
绝大多数(≥90%)的文献报道都同意大多数类型的二卤代N-杂芳烃的钯催化交叉偶联反应的区域化学结果。尽管典型选择性的机理基础已经确立，但几个例子表明，改变催化剂的位置可以改变选择性，从而产生非常规产品。在这个视角下，我们考察了这些不寻常的情况，在这些情况下，发散选择性受到配体或催化剂物种的控制。在某些情况下，反转选择性的机制起源已经确定，但在另一些情况下，机制仍不清楚。这一视角最后讨论了站点选择性交叉耦合领域的剩余挑战和机遇。这些措施包括更好地了解氧化加成机理，了解催化剂物种形成对选择性的作用，为环取代基对区域化学结果的影响建立一个解释，逆转一些“顽固的”底物类别的选择性，以及最大限度地减少二卤代和多卤代底物不必要的过度反应。
The vast majority (≥90%) of literature reports agree on the regiochemical outcomes of Pd-catalyzed cross-coupling reactions for most classes of dihalogenated N-heteroarenes. Despite a well-established mechanistic rationale for typical selectivity, several examples reveal that changes to the catalyst can switch site selectivity, leading to the unconventional product. In this Perspective, we survey these unusual cases in which divergent selectivity is controlled by ligands or catalyst speciation. In some cases, the mechanistic origin of inverted selectivity has been established, but in others the mechanism remains unknown. This Perspective concludes with a discussion of remaining challenges and opportunities for the field of site-selective cross-coupling. These include developing a better understanding of oxidative addition mechanisms, understanding the role of catalyst speciation on selectivity, establishing an explanation for the influence of ring substituents on regiochemical outcome, inverting selectivity for some “stubborn” classes of substrates, and minimizing unwanted over-reaction of di- and polyhalogenated substrates.
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影响因子：
15
作者：
Entz ED;Russell JEA;Hooker LV;Neufeldt SR
通讯作者：
Neufeldt SR
影响因子：
8.4
作者：
Cano R;Schmidt AF;McGlacken GP
通讯作者：
McGlacken GP
影响因子：
5.5
作者：
Bryan, Zachary J.;McNeil, Anne J.
通讯作者：
McNeil, Anne J.
用于低工作电压高效磷光OLED的含氮杂环材料
影响因子：
6.4
作者：
Chen, Dongcheng;Su, Shi-Jian;Cao, Yong
通讯作者：
Cao, Yong
DOI：
10.1039/b201789j
发表时间：
2002-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
Abraham, RJ;Reid, M
通讯作者：
Reid, M