Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp(3) )-H Bond Insertion.
Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp(3) )-H Bond Insertion.
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DOI：
10.1002/anie.202215163
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发表时间：
2023-01-26
影响因子：
16.6
通讯作者：
Pla-Quintana, Anna
中科院分区：
文献类型：
--
作者：
Diaz-Jimenez, Alex;Monreal-Corona, Roger;Poater, Albert;Alvarez, Maria;Borrego, Elena;Perez, Pedro J.;Caballero, Ana;Roglans, Anna;Pla-Quintana, Anna
The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp3)−H bond has been achieved for the first time during a silver‐catalyzed carbene/alkyne metathesis (CAM) process. A Tpx‐containing silver complex first promotes the generation of a donor‐acceptor silver carbene which triggers CAM, generating a subsequent donor‐donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp3)−H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C−H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step. The vinylogous position of a donor‐donor silver vinyl carbene is trapped with an aliphatic C(sp3)−H bond for the first time to afford 1‐benzoazepine scaffolds. The overall transformation entails a carbene alkyne metathesis of a donor‐acceptor silver carbene to furnish the key donor‐donor silver vinyl carbene whose vinylogous position is selectively intercepted in a stepwise C−H bond insertion.
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影响因子：
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通讯作者：
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