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

Diversification of pharmaceutical manufacturing processes: Taking the plunge into the non-PGM catalyst pool DOI Creative Commons
Hui Zhao, Anne K. Ravn, Michael C. Haibach

et al.

Published: March 22, 2024

Recent global events have led to the cost of platinum group metals (PGMs) reaching unprecedented heights. Many chemical companies are therefore starting seriously consider and evaluate if, where, they can substitute PGMs for non-PGMs in their catalytic processes. This review covers recent large-scale applications non-PGM catalysts modern pharmaceutical industry. By highlighting these selected successful examples non-PGM-catalyzed processes from literature, we hope emphasize enormous potential catalysis inspire further development within this field enable technology progress towards manufacturing We also present some historical context perceived advantages challenges implementing environment.

Language: Английский

Citations

1
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

1
N-heterocyclic carbene functionalized metal nanoparticles and nanoclusters for nanocatalysis DOI
Siyi Wang, Xianli Yu,

Yedong Wang

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Surface functionalization of metal materials with N-heterocyclic carbenes has emerged as an efficient avenue to prepare new and better nanocatalysts.

Language: Английский

Citations

1
Electrosynthesis of Iminophosphoranes: Accessing P(V) Ligands from P(III) Phosphines DOI Creative Commons
Velabo Mdluli, Dan Lehnherr, Yu‐hong Lam

et al.

Published: May 4, 2023

Iminophosphorane P(V) compounds are accessed via electrochemical oxidation of commercially available P(III) ligands, including mono-, di- and tri-dentate phosphines as well chiral phosphines. The reaction uses inexpensive bis(trimethylsilyl)carbodiimide an efficient safe aminating reagent. DFT calculations, cyclic voltammetry, NMR spectroscopic studies provide insight into the mechanism. proposed mechanism based on data reveals a special case sequential paired electrolysis, namely domino electrolysis process in which intermediates generated at cathode subsequently oxidized anode, followed by additional convergent process. calculations frontier orbitals iminophosphorane compared to those analogous phosphine oxides. This that N-cyano-iminophosphoranes have both higher HOMO lower LUMO than their oxide, rendering them suitable for sigma-donating pi-back-bonding.

Language: Английский

Citations

3
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