Synergistic LMCT and Ni Catalysis for Methylative Cross-Coupling Using tert-Butanol: Modulating Radical Pathways via Selective Bond Homolysis DOI
Lingfei Duan, Yunzhi Lin, Qing An

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present photocatalytic methylative cross-coupling reaction that capitalizes on synergistic interplay between LMCT and Ni catalysis, enabling use tert-butanol an efficient benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission tert-butanol, generating methyl is subsequently captured by catalytic cycle to form C-CH3 bonds. Under mild conditions, this affords methylation sp3 carbons adjacent carbonyls sp2 centers, demonstrating broad functional group tolerance applicability late-stage functionalization bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial tert-butanol-d10. This approach circumvents need traditional tert-butoxy precursors, such peroxides, while strategically pathway favor β-scission suppress unwanted formation solution. Mechanistic studies reveal plays crucial role facilitating generation, supporting concerted Ce-OR β-C-C homolysis mechanism, further evidenced modulation regioselectivity alkoxy radical-mediated β-scission.

Language: Английский

Iron-Catalyzed Ipso-Nitration of Aryl Borides via Visible-Light-Induced β-Homolysis DOI Creative Commons
Shuyang Liu, Yusheng Lu,

Hongyao Wang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3306 - 3313

Published: Feb. 7, 2025

Herein, we reported a practical method to realize ipso-nitration of boronic acids, their pinacol esters, and trifluoroborate salts with alkali metal salt NaNO3 as nitrating reagent. A FeIII/FeIV catalytic cycle involving an unusual visible-light-induced β-homolysis pathway the N–O bond in simple iron complex effectively provides nitryl radical key species. This protocol bears mild reaction conditions, broad scope (up 99% yield), good functional group compatibility, convenient scale-up synthesis.

Language: Английский

Citations

1
Iron–Cobalt Dual Catalysis for the Synthesis of Alkenyl Amino Acids and Modification of Peptides DOI

Huan-Huan Zhao,

Xu-Gang Zhang,

Haowen Jiang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 6, 2025

Herein, we report an Fe/Co dual-catalyzed strategy for synthesizing alkenyl unnatural amino acids and peptide modifications. This approach utilizes aspartic acid glutamic derivatives as alkyl radical precursors. It avoids the use of expensive photoredox catalysts substrate preactivation while preserving chirality acids. Furthermore, this enables both modification peptides synthesis amino-acid-based drug candidates boron-neutron capture therapy (BNCT).

Language: Английский

Citations

0
Synergistic LMCT and Ni Catalysis for Methylative Cross-Coupling Using tert-Butanol: Modulating Radical Pathways via Selective Bond Homolysis DOI
Lingfei Duan, Yunzhi Lin, Qing An

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present photocatalytic methylative cross-coupling reaction that capitalizes on synergistic interplay between LMCT and Ni catalysis, enabling use tert-butanol an efficient benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission tert-butanol, generating methyl is subsequently captured by catalytic cycle to form C-CH3 bonds. Under mild conditions, this affords methylation sp3 carbons adjacent carbonyls sp2 centers, demonstrating broad functional group tolerance applicability late-stage functionalization bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial tert-butanol-d10. This approach circumvents need traditional tert-butoxy precursors, such peroxides, while strategically pathway favor β-scission suppress unwanted formation solution. Mechanistic studies reveal plays crucial role facilitating generation, supporting concerted Ce-OR β-C-C homolysis mechanism, further evidenced modulation regioselectivity alkoxy radical-mediated β-scission.

Language: Английский

Citations

0