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

Aminoalkylation of Alkenes Enabled by Triple Radical Sorting DOI
William L. Lyon, Johnny Wang, Jesús Alcázar

et al.

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

Published: Jan. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Language: Английский

Citations

3

Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines DOI Creative Commons

Tian Hongjun,

Feng Jiang,

Xiaoming Wang

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(3)

Published: Jan. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Language: Английский

Citations

1

Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications DOI

Taotao Ling,

Jose M. Garfias,

S. Lawson

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134711 - 134711

Published: May 1, 2025

Language: Английский

Citations

0

Formation of Chiral All-Carbon Quaternary Stereocenters by Photoinduced Cobalt-Catalyzed Enantioselective Radical Coupling DOI
Yue Jia, Kai Zhang, Liang‐Qiu Lu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13550 - 13556

Published: Aug. 28, 2024

Photoinduced enantioselective strategies provide an efficient way to access chiral all-carbon quaternary stereocenters. Compared with the well-developed metal-catalyzed asymmetric conjugate addition of organometallic reagents enones, construction stereocenters through a radical process still remains challenging, especially for acyclic enones due their enhanced conformational mobility. Herein, we disclose photoinduced cobalt-catalyzed coupling α,β-unsaturated 2-acyl imidazoles and α-silylamines give β,β-disubstituted γ-amino acid derivatives carbon The facile protocol shows good functional group tolerance broad substrate scope. corresponding products were obtained in generally yields (up 96%) high enantioselectivities 99:1 e.r.).

Language: Английский

Citations

2

Asymmetric radical allylation of β-keto esters with vinyl cyclopropanes by dual photoredox/nickel catalysis DOI

Wen-Yuan Qu,

Xue‐Song Zhou,

Wen‐Jing Xiao

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(11), P. 3807 - 3816

Published: Aug. 27, 2024

Language: Английский

Citations

2

Copper(I)-Catalyzed Enantioselective α-Alkylation of 2-Acylimidazoles DOI
Zong‐Ci Liu, Hongming Zhang, Yi Li

et al.

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

Published: Dec. 3, 2024

Catalytic asymmetric α-alkylation of simple carboxylic acid derivatives is a challenging issue due to the difficulties in achieving high catalytic efficiency and controlling enantioselectivity. Herein, by using copper(I)-(R)-DTBM-SEGPHOS complex as catalyst 2-acylimidazoles pronucleophiles, general method for accomplished. Various alkyl electrophiles, including allyl bromides, benzyl propargyl bromide, unactivated sulfonates, serve efficient alkylation reagents. The reaction enjoys advantages an easy protocol, good functional group tolerance, 2,4,6-Trimethylphenol found effective additive increase yields. Preliminary 1H NMR experiments indicate precoordination copper(I) catalyst, which might acidify α-hydrogens allow facile generation stabilized enolates. Finally, synthetic utility present demonstrated formal synthesis AZD2716, potent secreted phospholipase A2 inhibitor.

Language: Английский

Citations

2

Enantioselective Decarboxylative C(sp3)-C(sp3) Cross-Coupling of Aliphatic Acids with gem-Borazirconocene Alkanes DOI Creative Commons
Jing Wang,

Songlin Bai,

Chao Yang

et al.

Published: June 13, 2024

Asymmetric decarboxylative cross-couplings of carboxylic acids represent a powerful tool to synthesize chiral building blocks for medicinal chemistry and material science. However, synthesis versatile alkylboron derivatives via asymmetric C(sp3)-C(sp3) cross-coupling from readily available primary aliphatic mild organometallic reagents is still challenging. In this study, we report visible-light-induced, Ni-catalyzed enantioconvergent unactivated with gem-borazirconocene alkanes, furnishing diverse array valuable blocks. The broad substrate scope, high functional group tolerance, the late-stage modification complex drug molecules natural products enantioselectivity demonstrate synthetic potential method. Mechanistic investigations suggest an radical-radical pathway, wherein radical generated through single-electron reduction ZrIII species, representing unprecedented example enantioselective cross coupling in absence photocatalysts.

Language: Английский

Citations

1

Cost‐Effective Carbon Quaternization with Redox‐Active Esters and Olefins DOI

Sudhir Kumar Hota,

Sandip Murarka

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 10, 2024

Quaternary carbons are embedded in various natural products, pharmaceuticals, and organic materials. However, constructing this valuable motif is far from trivial. Conventional approaches mainly rely on classical polar disconnections encounter bottlenecks concerning harsh conditions, functional group tolerance, regioselectivity, step economy. In context, Kawamata, Baran, Shenvi, co-workers recently demonstrated that two feedstock chemicals, alkyl carboxylic acids olefins, could be utilized to construct tetrasubstituted the presence of an inexpensive iron porphyrin catalyst a suitable reductant combination through quaternization radical intermediates. The method enables access sterically encumbered quaternary under mild robust conditions. Taking complete detour conventional approaches, present heteroselective radical-radical coupling simplifies synthesis carbon-containing molecules innovative distinctive disconnection approach.

Language: Английский

Citations

1

Bimolecular Homolytic Substitution (SH2) at A Transition Metal DOI
Ying Zhang, Kai‐Dian Li, Huan‐Ming Huang

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: Aug. 8, 2024

Abstract Transition metal‐catalyzed cross‐coupling reactions have become a powerful and widely used synthetic approach for the construction of both carbon‐carbon carbon‐heteroatom bonds. These revolutionized chemistry by enabling efficient formation complex molecular architectures. Among various methods available, bimolecular homolytic substitution (S H 2) reaction has emerged as an attractive versatile method C(sp 3 )−C(sp ) )‐heteroatom In recent years, significant progress been made in development radical S 2 reactions, particularly those involving different transition metal complexes such cobalt, nickel, iron. advancements expanded scope allowing greater diversity substrate compatibility conditions. this review, we aim to highlight latest breakthroughs mechanistic insights into focusing on role catalysts facilitating these transformations. We will discuss types that employed, pathways involved, potential applications synthesis organic molecules.

Language: Английский

Citations

1

Enantioselective Decarboxylative C(sp3)-C(sp3) Cross-Coupling of Aliphatic Redox-Active Esters with gem-Borazirconocene Alkanes DOI
Jing Wang,

Songlin Bai,

Chao Yang

et al.

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

Published: Sept. 17, 2024

Asymmetric decarboxylative cross-couplings of carboxylic acids are powerful methods for synthesizing chiral building blocks essential in medicinal chemistry and material science. Despite their potential, creating versatile alkylboron derivatives through asymmetric C(sp

Language: Английский

Citations

1