A Cooperative Rhodium/Secondary Phosphine Oxide [Rh/P(O)nBu2] Template for Catalytic Hydrodefluorination of Perfluoroarenes DOI Creative Commons
Wei‐Chieh Chang, Helena Randel, Thomas Weyhermüller

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 1, 2023

The selective activation of C-F bonds under mild reaction conditions remains an ongoing challenge bond activation. Here, we present a cooperative [Rh/P(O)nBu2 ] template for catalytic hydrodefluorination (HDF) perfluoroarenes. In addition to substrates presenting electron-withdrawing functional groups, the system showed exceedingly rare tolerance electron-donating functionalities and heterocycles. high chemoselectivity catalyst its readiness be deployed at preparative scale illustrate practicality. Empirical mechanistic studies density theory (DFT) study have identified rhodium(I) dihydride complex as catalytically relevant species determining role phosphine oxide fragment. Altogether, demonstrate that molecular templates based on these design elements can assembled create catalysts with increased reactivity challenging activations.

Language: Английский

Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings DOI

Ni Xiong,

Yang Li, Rong Zeng

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1678 - 1685

Published: Jan. 13, 2023

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and copper catalyst delivered enabled subsequent coupling reactions form C–N or C–C bonds. By merging iron-catalyzed with catalysis, this system allows smooth conversion wide range acids amination, decarboxylative dehydrogenation, alkylation efficiently. A variety complex drug natural molecules is applicable, suggesting that would facilitate rapid compound library synthesis benefit discovery pharmaceutical agents.

Language: Английский

Citations

66
Contemporary Approaches for Amide Bond Formation DOI
Paola Acosta‐Guzmán, Andrea Ojeda‐Porras, Diego Gamba‐Sánchez

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4359 - 4391

Published: Nov. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Language: Английский

Citations

46
Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes DOI
Till Schmidt‐Räntsch, Hendrik Verplancke, Jonas N. Lienert

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(9)

Published: Dec. 14, 2021

C-H amination and amidation by catalytic nitrene transfer are well-established typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion (formal) terminal nitride ligands into bonds is much less developed nitrogen atom remains unknown. We here report synthesis a formal complex palladium. Photocrystallographic, magnetic, computational characterization support assignment as an authentic metallonitrene (Pd-N) with diradical ligand that singly bonded to Pd

Language: Английский

Citations

59
Adaptive Catalytic Systems for Chemical Energy Conversion DOI Creative Commons
Alexis Bordet, Walter Leitner

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 22, 2023

Abstract The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room disruptive innovations regarding production processes. fluctuation variability associated with non‐fossil energy raw material supply holds many challenges catalysts to cope the resulting dynamics. However, new opportunities also arise once catalyst design starts aim at performance that is “adaptive” rather than “task‐specific”. In this Scientific Perspective, we propose define adaptivity in catalysis on basis three properties are reversibility, rapidity, robustness ( R 3 rule). Promising strategies selected examples described substantiate scientific concept highlight its potential conversion.

Language: Английский

Citations

29
Mild Amide Synthesis Using Nitrobenzene under Neutral Conditions DOI

Ni Xiong,

Yuanqi Dong,

Bin Xu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(26), P. 4766 - 4771

Published: June 27, 2022

Amide synthesis is one of the most important transformations in organic chemistry due to broad application pharmaceutical drugs and materials. In this report, we describe a mild protocol for amide formation using readily available nitroarenes as nitrogen sources an inexpensive iron complex catalyst. Because use pH-neutral conditions avoidance strong oxidant or reductant, wide range aromatic aliphatic aldehydes well with various functional groups could be tolerated well. A plausible mechanism proposed based on detailed studies, which catalyst initiates radical process solvent plays key role O-atom acceptor.

Language: Английский

Citations

36
Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation DOI Creative Commons
Emanuele Antico, Peter Schlichter, Christophe Werlé

et al.

JACS Au, Journal Year: 2021, Volume and Issue: 1(6), P. 742 - 749

Published: May 11, 2021

The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO)5] as catalyst and bench stable PhSiH3 reducing agent. It shown that reaction with earth-abundant metal could be performed either a loading low 0.5 mol %, rare use [MnBr(CO)5], or on gram scale employing only 1.5 equiv PhSiH3, lowest amount silane reported date for this transformation. Kinetic data control experiments have provided initial insight into mechanism catalytic process, suggesting it proceeds via formation silyl ester intermediates ligand dissociation generate coordinatively unsaturated Mn(I) complex active species.

Language: Английский

Citations

35
An Adaptive Rhodium Catalyst to Control the Hydrogenation Network of Nitroarenes DOI Creative Commons
Vishal Chugh, Basujit Chatterjee, Wei‐Chieh Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 27, 2022

An adaptive catalytic system that provides control over the nitroarene hydrogenation network to prepare a wide range of aniline and hydroxylamine derivatives is presented. This takes advantage delicate interplay between rhodium(III) center Lewis acidic borane introduced in secondary coordination sphere metal. The high chemoselectivity catalyst presence various potentially vulnerable functional groups its readiness be deployed at preparative scale illustrate practicality. Mechanistic studies density theory (DFT) methods were used shed light on mode functioning elucidate origin adaptivity. competition for interaction with boron solvent molecule substrate was found crucial When operating THF, reduction stops platform, whereas reaction can directed platform toluene.

Language: Английский

Citations

23
Catalyst‐Free Photooxidative N‐Acylation of Azoles with Aldehydes DOI

Nianfeng Gong,

Zelin Zhao,

David James Young

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract A catalyst‐free photochemical N‐acylation of azoles with aldehydes has been developed using inexpensive BrCCl 3 as the oxidant. This transition‐metal‐ and photocatalyst‐free amidation proceeded efficiently a wide variety substrates to give corresponding N‐acylazoles, including for late modification pharmaceutically active molecules, on gram‐scale.

Language: Английский

Citations

0
Rapid Synthesis of Primary Amides Using Ammonia Borane DOI
Xiaoyun Li, Jiaxin Kang, Hui Han

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1720 - 1726

Published: Jan. 23, 2025

We report the rapid synthesis of primary amides by directly using commercially available ammonia borane (NH3·BH3), sodium hexamethyldisilazide (NaHMDS), and esters. The success this protocol relies on NH3·BH3 as nitrogen source being considerably more convenient NaHMDS an excellent proton abstractor but not participating in nucleophilic addition reaction. reaction had a wide substrate scope containing bioactive molecules, most substrates were efficiently amidated over 90% yields.

Language: Английский

Citations

0
Palladium-Catalyzed Divergent Synthesis from o-Sulfonamido Trifluoroacetophenones and 2-En-4-ynyl Carbonates DOI

Meng-Qi Gan,

Jian‐Xiang Zhu,

Zhichao Chen

et al.

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

Published: Feb. 15, 2025

Here we present a palladium-catalyzed divergent transformative reaction between o-sulfonamido trifluoroacetophenones and 2-en-4-ynyl carbonates. A spectrum of enantioenriched 2,5-dihydrofuran-fused tetrahydroquinolines bearing either (Z)- or (E)-exocyclic double bond are constructed with moderate to high enantioselectivity from 5-aryl-substituted carbonates by tuning palladium sources, while analogous 2,3-dihydrofuran-fused products furnished using 5-alkyl-substituted ones.

Language: Английский

Citations

0