Photochemical Metal‐Hydride Hydrogen Atom Transfer Mediated Radical Hydrofunctionalization of Dienes and Allenes DOI

Huaipu Yan,

Jing‐Ran Shan, Lei Shi

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(2)

Published: Nov. 17, 2023

The metal-hydride hydrogen atom transfer (MHAT) method is widely recognized as a powerful technique for functionalizing alkenes. However, its application in the functionalization of industrial feedstock dienes and allenes relatively rare due to challenges related chemo-selectivity. In recent studies, Co-porphines have been identified highly efficient catalysts under photoirradiation MHAT, demonstrating an exceptional level chemoselectivity allenes, while disregarding other simple olefins present. This novel enables selective reductive coupling pyridines with allylation aldehydes by combination Ti catalysis. Mechanistic studies density functional theory (DFT) calculations support idea that non-reversible atoms from cobalt hydride leading generation allyl radicals, key step catalytic cycle.

Language: Английский

Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions DOI Creative Commons
Chang‐Yin Tan, Sungwoo Hong

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Language: Английский

Citations

2
Mimicking hydrogen-atom-transfer-like reactivity in copper-catalysed olefin hydrofunctionalization DOI
Jun‐Jie Wang, He Huang, Han‐Li Sun

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(7), P. 838 - 846

Published: July 1, 2024

Language: Английский

Citations

2
Photoredox‐catalyzed Decyanative Radical Cross‐coupling Reactions of Aromatic Nitriles DOI
Fei Chao,

Haibin Yang,

Yanxiong Fang

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(5)

Published: Nov. 27, 2023

Abstract (Hetero)arenes are one kind of important structural motifs existed extensively in clinical pharmaceutics, pesticides, and so on. Developing novel method for introducing (hetero)aryl group through the employment cheap abundant feedstocks has attracted considerable attentions from synthetic community. In this review, we summarize recent advancements photoredox‐catalyzed decyanative cross‐coupling reactions based on persistent aromatic nitrile‐derived radical. We separate review into redox‐neutral reductive according to whether an external reducing agent is required. The diverse strategies overcoming redox potential limitation photocatalyst emphasized discussion specific reaction.

Language: Английский

Citations

6
Photoinduced cobalt catalysis for the reductive coupling of pyridines and dienes enabled by paired single-electron transfer DOI Creative Commons

Jingyang Qin,

Manuel Barday,

Samikshan Jana

et al.

Published: May 29, 2023

The development of methods to form C–C bonds from readily-available starting materials is essential in driving innovation functional molecules. In this context, hydrofunctionalisation feedstock alkenes via catalytic hydrogen atom transfer an earth-abundant metal can be effective and efficient approach. However, the range amenable coupling partners for bond formation predominantly limited strongly electrophilic radical traps. Here, we report alternative approach: simultaneous key cobalt-hydride intermediate persistent easily-synthesised pyridyl phosphonium salts enabled through paired, photoinduced single-electron transfer. This facilitates selective dienes styrenes a traceless manner at C4-position wide-range pyridine substrates. mildness method underscored by its group tolerance demonstrated applications late-stage-functionalisation drugs. Based on combination experimental computational studies, propose mechanistic pathway which proceeds non-reversible cobalt hydride species uniquely presence other olefins.

Language: Английский

Citations

4
Photochemical Metal‐Hydride Hydrogen Atom Transfer Mediated Radical Hydrofunctionalization of Dienes and Allenes DOI

Huaipu Yan,

Jing‐Ran Shan, Lei Shi

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(2)

Published: Nov. 17, 2023

The metal-hydride hydrogen atom transfer (MHAT) method is widely recognized as a powerful technique for functionalizing alkenes. However, its application in the functionalization of industrial feedstock dienes and allenes relatively rare due to challenges related chemo-selectivity. In recent studies, Co-porphines have been identified highly efficient catalysts under photoirradiation MHAT, demonstrating an exceptional level chemoselectivity allenes, while disregarding other simple olefins present. This novel enables selective reductive coupling pyridines with allylation aldehydes by combination Ti catalysis. Mechanistic studies density functional theory (DFT) calculations support idea that non-reversible atoms from cobalt hydride leading generation allyl radicals, key step catalytic cycle.

Language: Английский

Citations

4