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O-H bond activation of β,γ-unsaturated oximes via hydrogen atom transfer (HAT) and photoredox dual catalysis.

ABSTRACT: Hydrogen atom transfer (HAT) and photoredox dual catalysis provides a unique opportunity in organic synthesis, enabling the direct activation of C/Si/S-H bonds. However, the activation of O-H bonds of β,γ-unsaturated oximes poses a challenge due to their relatively high redox potential, which exceeds the oxidizing capacity of most currently developed photocatalysts. We here demonstrate that the combination of HAT and photoredox catalysis allows the activation of O-H bond of β,γ-unsaturated oximes. The strategy effectively addresses the oxime's high redox potential and offers a universal pathway for iminoxyl radical formation. Leveraging the versatility of this approach, a diverse array of valuable heterocycles have been synthesized with the use of different radical acceptors. Mechanistic studies confirm a HAT process for the O-H bond activation.

SUBMITTER: Yi L

PROVIDER: S-EPMC10718179 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

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O-H bond activation of β,γ-unsaturated oximes via hydrogen atom transfer (HAT) and photoredox dual catalysis.

Yi Liang L Zhu Chen C Chen Xiangyu X Yue Huifeng H Ji Tengfei T Ma Yiqiao Y Cao Yuanyuan Y Kancherla Rajesh R Rueping Magnus M

Chemical science 20231130 48

Hydrogen atom transfer (HAT) and photoredox dual catalysis provides a unique opportunity in organic synthesis, enabling the direct activation of C/Si/S-H bonds. However, the activation of O-H bonds of β,γ-unsaturated oximes poses a challenge due to their relatively high redox potential, which exceeds the oxidizing capacity of most currently developed photocatalysts. We here demonstrate that the combination of HAT and photoredox catalysis allows the activation of O-H bond of β,γ-unsaturated oxime ...[more]

PMID: 38098711

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