Palladium-Catalyzed Carbonylative Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates.
Palladium-Catalyzed Carbonylative Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates.
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由不稳定烯醇引发的钯催化未活化烯烃的羰基双官能化。
DOI：
10.1002/anie.202307455
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Newhouse,TimothyR
中科院分区：
文献类型：
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作者：
Zhang,Pengpeng;Newhouse,TimothyR
本报告描述了由烯醇化亲核试剂引发的未活化烯烃的钯催化羰基化双官能化的第一个例子。该方法涉及在大气压CO下通过不稳定的烯醇化亲核试剂引发，并用碳亲电试剂终止。该方法与各种亲电试剂相容，包括芳基、杂芳基和乙烯基碘，以产生合成有用的1，5-二酮产物，其被证明是多取代吡啶的前体。观察到具有两个桥接CO单元的PdI-二聚体络合物，尽管其在催化中的作用尚未了解。
This report describes the first example of palladium‐catalyzed carbonylative difunctionalization of unactivated alkenes initiated by enolate nucleophiles. The approach involves initiation by an unstabilized enolate nucleophile under an atmospheric pressure of CO and termination with a carbon electrophile. This process is compatible with a diverse range of electrophiles, including aryl, heteroaryl, and vinyl iodides to yield synthetically useful 1,5‐diketone products, which were demonstrated to be precursors for multi‐substituted pyridines. A PdI‐dimer complex with two bridging CO units was observed although its role in catalysis is not yet understood.