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Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp³ )-H Bond Insertion.

ABSTRACT: 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 Tp^x -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.

SUBMITTER: Diaz-Jimenez A

PROVIDER: S-EPMC10108323 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

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Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3 )-H Bond Insertion.

Díaz-Jiménez Àlex À Monreal-Corona Roger R Poater Albert A Álvarez María M Borrego Elena E Pérez Pedro J PJ Caballero Ana A Roglans Anna A Pla-Quintana Anna A

Angewandte Chemie (International ed. in English) 20221222 5

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 t ...[more]

PMID: 36345831

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