Benzothiazolium Salts as Versatile Primary Alcohol Derivatives in Ni-Catalyzed Cross-Electrophile Arylation/Vinylation DOI

Cheng Ye,

Quan Lin,

Yunrong Chen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

A Ni-catalyzed cross-electrophile coupling of aryl/vinyl halides with benzothiazolium salts derived from alcohols is presented.

Language: Английский

Towards a sustainable tomorrow: advancing green practices in organic chemistry DOI
Sudripet Sharma, Fabrice Gallou, Sachin Handa

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6289 - 6317

Published: Jan. 1, 2024

Chemistry in water, leveraging its solvent properties, provides a safer and more sustainable alternative to traditional organic methods.

Language: Английский

Citations

23
Finding suitable biobased solvents for extractions from water DOI Creative Commons
Gerhard König, Pascal Hauk, Fabrice Gallou

et al.

RSC Sustainability, Journal Year: 2025, Volume and Issue: 3(3), P. 1539 - 1549

Published: Jan. 1, 2025

Solvent usage is one of the most critical factors for carbon footprint chemical and pharmaceutical industries, with profound consequences an undesirable or sub-optimal selection.

Language: Английский

Citations

1
Cross-Electrophile Coupling to Form Sterically Hindered C(sp2)–C(sp3) Bonds: Ni and Co Afford Complementary Reactivity DOI
Tung-Kung Wu, Anthony J. Castro,

Kasturi Ganguli

et al.

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

Published: March 7, 2025

The formation of sterically hindered C(sp2)-C(sp3) bonds could be a useful synthetic tool but has been understudied in cross-electrophile coupling. Here, we report two methods that couple secondary alkyl bromides with aryl halides contain C-X bonds: 1) ortho-substituted nickel catalysts and 2) di-ortho-substituted iodides cobalt catalysts. Stoichiometric experiments deuterium labeling studies show [Co] is better than [Ni] for oxidative addition Ar-I radical capture/reductive elimination steps arenes. For both metals, Ar-H side products observed reactions low-yielding appear to arise from Ar• hydrogen-atom transfer the solvent. While origins differences scope are not yet understood, these demonstrate previously unknown complementarity between

Language: Английский

Citations

0
6‐Hydroxy Picolinohydrazides Promoted Cu(I)‐Catalyzed Hydroxylation Reaction in Water: Machine‐Learning Accelerated Ligands Design and Reaction Optimization DOI
Lanting Xu, Jiazhou Zhu, Xiaodong Shen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(52)

Published: Aug. 27, 2024

Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small-molecule pharmaceuticals and serve as versatile intermediates synthetic organic chemistry. Herein, we report an efficient Cu(I)/6-hydroxy picolinohydrazide-catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) water. By establishing machine learning (ML) models, the design ligands optimization conditions were effectively accelerated. The N-(1,3-dimethyl-9H- carbazol-9-yl)-6-hydroxypicolinamide (L32, 6-HPA-DMCA) demonstrated high efficiency for bromides, promoting reactions with a minimal catalyst loading 0.01 mol % (100 ppm) at 80 °C to reach 10000 TON; substrates containing sensitive functional groups, needs be increased 3.0 under near-room temperature conditions. N-(2,7-Di-tert-butyl-9H-carbazol-9-yl)-6-hydroxypicolinamide (L42, 6-HPA-DTBCA) displayed superior activity chloride substrates, enabling 100 2-3 loading. These represent state art both lowest copper-catalyzed reactions. Furthermore, this method features sustainable environmentally friendly solvent system, accommodates wide range shows potential developing robust scalable synthesis processes key pharmaceutical intermediates.

Language: Английский

Citations

2
Micelle-Enabled Hofmann Rearrangement in Water DOI

Xiaoqi Xing,

Kangming Zhao,

Zhidong Li

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(7), P. 2945 - 2950

Published: June 28, 2024

An environmentally sustainable approach for the Hofmann rearrangement was developed. The presence of nanomicelles allows such a transformation to proceed smoothly in mild conditions with water as sole reaction medium compared traditional methods, which use significant amounts organic solvents. A variety amides containing functional groups have been constructed under these conditions, affording compounding amine product good excellent yields (up 99%). process scaled up and proven be robust its implementation synthesis pharmaceutically relevant compounds.

Language: Английский

Citations

0
Micelle Enabled Buchwald‐Hartwig Amination in Water with the Bening by Design Surfactant TPGS‐750‐M for the Synthesis of the JAK Inhibitor 4‐((2‐Chlorophenyl)amino)‐6‐((6‐methylpyridin‐2‐yl)amino)nicotinamide DOI
Hao Jiang, Bin Wu,

Dominik Rufle

et al.

Helvetica Chimica Acta, Journal Year: 2024, Volume and Issue: 107(9)

Published: Aug. 11, 2024

Abstract An efficient and scalable Buchwald‐Hartwig amination towards the synthesis of API candidate 4‐((2‐Chlorophenyl)amino)‐6‐((6‐methylpyridin‐2‐yl)amino)nicotinamide as a JAK inhibitor was described. The process developed using water water‐miscible co‐solvent. It facilitated by benign design surfactant TPGS‐750‐M, that promoted robust reliable preparation our target compound in high yields, with improved reaction profile via an operationally simple protocol.

Language: Английский

Citations

0
6‐Hydroxy Picolinohydrazides Promoted Cu(I)‐Catalyzed Hydroxylation Reaction in Water: Machine‐Learning Accelerated Ligands Design and Reaction Optimization DOI
Lanting Xu, Jiazhou Zhu, Xiaodong Shen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(52)

Published: Aug. 27, 2024

Abstract Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small‐molecule pharmaceuticals and serve as versatile intermediates synthetic organic chemistry. Herein, we report an efficient Cu(I)/6‐hydroxy picolinohydrazide‐catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) water. By establishing machine learning (ML) models, the design ligands optimization conditions were effectively accelerated. The N ‐(1,3‐dimethyl‐9 H ‐ carbazol‐9‐yl)‐6‐hydroxypicolinamide ( L32 , 6‐HPA‐DMCA) demonstrated high efficiency for bromides, promoting reactions with a minimal catalyst loading 0.01 mol % (100 ppm) at 80 °C to reach 10000 TON; substrates containing sensitive functional groups, needs be increased 3.0 under near‐room temperature conditions. ‐(2,7‐Di‐ tert ‐butyl‐9 ‐carbazol‐9‐yl)‐6‐hydroxypicolinamide L42 6‐HPA‐DTBCA) displayed superior activity chloride substrates, enabling 100 2–3 loading. These represent state art both lowest copper‐catalyzed reactions. Furthermore, this method features sustainable environmentally friendly solvent system, accommodates wide range shows potential developing robust scalable synthesis processes key pharmaceutical intermediates.

Language: Английский

Citations

0
Benzothiazolium Salts as Versatile Primary Alcohol Derivatives in Ni-Catalyzed Cross-Electrophile Arylation/Vinylation DOI

Cheng Ye,

Quan Lin,

Yunrong Chen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

A Ni-catalyzed cross-electrophile coupling of aryl/vinyl halides with benzothiazolium salts derived from alcohols is presented.

Language: Английский

Citations

0