Determination of pKa values of C‐H bonds in polar fluorinated arenes referred to a new CF3SO2‐substituted anchor compound DOI
Xiangmei Kong, Y. Liang,

Zhenbo Guo

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

Abstract p K a values of C−H bonds remain unreported and challenging in fluorous solvents because these solvents’ unique physicochemical properties, although they have been measured, theorized predicted successfully water common organic solvents. Herein, new CF 3 SO 2 ‐substituted anchor compound designed for matching the properties polar fluorinated arenes is synthesized. Its self‐dissociation constants are used as bases experimentally determining 36 compounds them. These determined exhibit excellent linear free‐energy relationships correlate well with their corresponding DFT‐calculated values. data indicate that thermodynamically more favorable deprotonation ketone derivatives than acetonitrile reaction media, resulting enhanced deprotonation‐promoted CO fixation. The this work can be an important guidance tool reactions involving formation cleavage arenes.

Language: Английский

Photoinduced Regiodivergent and Enantioselective Cross-Coupling of Glycine Derivatives with Hydrocarbon Feedstocks DOI
Fuxing Yang,

Longxiao Chi,

Ziqi Ye

et al.

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

Published: Jan. 2, 2025

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from single set starting materials, significantly enriching their enantiomeric composition. However, design radical-mediated regiodivergent and enantioselective reactions that can accommodate wide range functional groups substrates has posed significant challenges. The obstacles primarily lie in switching regioselectivity achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed new catalytic system integrates photoinduced hydrogen atom transfer (HAT) copper catalysis, involving fine-tuning ligands, additives, other reaction parameters. facilitates cross-couplings between N-aryl glycine ester/amide derivatives abundant hydrocarbon feedstocks through strong C(sp3)–H bond activation. This approach allows controlled stereoselective formation C(sp3)–C(sp3) C(sp3)–N bonds, yielding rich variety C- or N-alkylated esters amides commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), enantioselectivities 96% ee). Our methodology not only provides promising avenue incorporation alkyl functionalities onto specific sites biologically molecules but also offers practical while simultaneously induction within photochemical reactions.

Language: Английский

Citations

9
Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis DOI

Xiang‐Kui He,

Liang‐Qiu Lu,

Bao-Ru Yuan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

Citations

18
Recent advances in C(sp3)–N bond formation via metallaphoto-redox catalysis DOI
Juan Zhang,

Xiao-Die Huan,

Xin Wang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(50), P. 6340 - 6361

Published: Jan. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Language: Английский

Citations

14
Manganese Complexes with Consecutive Mn(IV) → Mn(III) Excitation for Versatile Photoredox Catalysis DOI
Tao Huang,

Pangang Du,

Xiuliang Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24515 - 24525

Published: July 30, 2024

Manganese complexes stand out as promising candidates for photocatalyst design, attributed to their eco- and biocompatibility, versatile valence states, capability facilitating multiple electronic excitations. However, several intrinsic constraints, such inadequate visible light response short excited-state lifetimes, hinder effective photoinduced electron transfer impede photoredox activation of substrates. To overcome this obstacle, we have developed a class manganese featuring boron-incorporated

Language: Английский

Citations

5
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

4
Aldehyde–Olefin Couplings Via Sulfoxylate-Mediated Oxidative Generation of Ketyl Radical Anions DOI Creative Commons
Zhihang Li,

Joseph A. Tate,

Adam Noble

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 20, 2024

Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction a nucleophilic radical. However, this pathway is challenging due the large negative potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe development an alternative strategy access ketyl from aldehydes, which avoids by instead proceeding via oxidation and desulfination α-hydroxy sulfinates. These redox-active aldehyde adducts generated

Language: Английский

Citations

4
p-Diarylboryl Halothiophenols as Multifunctional Catalysts via Photoactive Intramolecular Frustrated Lewis Pairs DOI

Takeru Kikura,

Y. B. Taura,

Yoshitaka Aramaki

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20425 - 20431

Published: July 8, 2024

p-Diarylboryl halothiophenols are developed and unequivocally characterized. Their photophysical properties catalytic performance unveiled by experimental theoretical investigations. This novel class of triarylboranes behaves as a Brønsted acid to generate the corresponding borylthiophenolate that can absorb visible light undergo intramolecular charge transfer form radical pair consisting boron anion thiyl radical, which acts single-electron reductant while engaging in hydrogen atom regenerate parent borylthiophenol. The synthetic relevance this mode action is demonstrated establishment unique catalysis integrates three different yet tunable functions single cycle, thereby allowing borylthiophenols solely promote assembly sterically congested 1,2-diols 1,2-aminoalcohol derivatives via radical–radical cross-coupling.

Language: Английский

Citations

3
Photoredox-mediated cobalt catalysis for non-asymmetric and asymmetric synthesis DOI Creative Commons

Zhiyong Chi,

Yuhang He,

Ablimit Abdukader

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102613 - 102613

Published: May 1, 2025

Language: Английский

Citations

0
A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition DOI

Chengxi Zhang,

Xianqing Wu, Jingping Qü

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Language: Английский

Citations

3
Cobalt-Catalyzed Asymmetric Migratory Nozaki–Hiyama–Kishi Coupling DOI
Jian Chen,

Lifu Wu,

Zhiyong Song

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

Selective functionalization of ubiquitous C-H bonds based on 1,

Language: Английский

Citations

3