Ligand-Enabled Palladium-Catalyzed β-C(sp3)–H Biarylation of Native Amides with Cyclic Diaryliodonium Salts DOI
Animesh Das,

Mohit Chotia,

Biplab Maji

et al.

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

Published: May 2, 2025

Herein, we report a Pd-catalyzed β-C(sp3)-H biarylation of native amides using diaryliodonium salts. A pyridine-3-sulfonic acid ligand that might stabilize the substrate-bound palladium species was found to be essential for high catalytic activity. The reaction displayed broad scope and showed excellent compatibility with diverse cyclic salts amide substrates. retained iodo functionality on product provides versatile handle further increasing molecular complexity.

Language: Английский

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

Citations

150
Transient directing ligands for selective metal-catalysed C–H activation DOI
Nupur Goswami, Trisha Bhattacharya, Debabrata Maiti

et al.

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(9), P. 646 - 659

Published: July 20, 2021

Language: Английский

Citations

100
The emergence of the C–H functionalization strategy in medicinal chemistry and drug discovery DOI
Ranjan Jana, Hasina Mamataj Begam,

Enakshi Dinda

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10842 - 10866

Published: Jan. 1, 2021

Owing to the market competitiveness and urgent societal need, an optimum speed of drug discovery is important criterion for successful implementation. Despite rapid ascent artificial intelligence computational bioanalytical techniques accelerate in big pharma, organic synthesis privileged scaffolds predicted silico vitro vivo studies still considered as rate-limiting step. C-H activation latest technology added into chemist's toolbox construction late-stage modification functional molecules achieve desired chemical physical properties. Particularly, elimination prefunctionalization steps, exceptional group tolerance, complexity-to-diversity oriented synthesis, functionalization medicinal expand space. It has immense potential a library molecules, structural required pharmacological properties such absorption, distribution, metabolism, excretion, toxicology (ADMET) attachment reporters proteome profiling, metabolite etc. preclinical studies. Although heterocycle modification, 18F labelling, methylation, via have been reviewed from synthetic standpoint, general overview these protocols aspects not reviewed. In this feature article, we will discuss recent trends methodologies through activation/annulation cascade; arylation sp2-sp2 sp2-sp3 cross-coupling; borylation/silylation introduce linchpin further manipulation; amination N-heterocycles hydrogen bond acceptors; fluorination/fluoroalkylation tune polarity lipophilicity; methylation: methyl magic discovery; peptide macrocyclization therapeutics biologics; fluorescent labelling radiolabelling bioimaging; bioconjugation biology studies; drug-metabolite biodistribution excretion diversification drug-molecules increase efficacy safety; cutting-edge DNA encoded improved chemistry discovery.

Language: Английский

Citations

92
C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives DOI
Lukass Lukasevics, Aleksandrs Cizikovs, Liene Grigorjeva

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10827 - 10841

Published: Jan. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Language: Английский

Citations

69
A Guide to Directing Group Removal: 8‐Aminoquinoline DOI
Liam S. Fitzgerald, Miriam L. O’Duill

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(33), P. 8411 - 8436

Published: Feb. 10, 2021

The use of directing groups allows high levels selectivity to be achieved in transition metal-catalyzed transformations. Efficient removal these auxiliaries after successful functionalization, however, can very challenging. This review provides a critical overview strategies used for Daugulis' 8-aminoquinoline (2005-2020), one the most widely N,N-bidentate groups. limitations are discussed and alternative approaches suggested challenging substrates. Our aim is provide comprehensive end-users' guide chemists academia industry who want harness synthetic power groups-and able remove them from their final products.

Language: Английский

Citations

57
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

39
Hydrogen-bond-acceptor ligands enable distal C(sp3)–H arylation of free alcohols DOI
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park

et al.

Nature, Journal Year: 2023, Volume and Issue: 622(7981), P. 80 - 86

Published: Sept. 6, 2023

Language: Английский

Citations

29
Unified approaches in transition metal catalyzed C(sp3)–H functionalization: recent advances and mechanistic aspects DOI
Jagrit Grover,

Amal Tom Sebastian,

S.K. Maiti

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Direct alteration of unactivated C–H bonds organic building blocks.

Language: Английский

Citations

1
Nickel-catalyzed C(sp2)–H alkynylation of free α-substituted benzylamines using a transient directing group DOI

Xinghao Cai,

Chen Ma, Ying Kang

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110901 - 110901

Published: Jan. 1, 2025

Language: Английский

Citations

1
Dual Relay Rh-/Pd-Catalysis Enables β-C(sp3)-H Arylation of α-Substituted Amines DOI Creative Commons
Shuailong Li, Sani Yahaya, Jan Bojanowski

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A dual relay catalytic protocol, built on reversible dehydrogenation of amines by Rh catalysis and C-H functionalisation transient imines Pd catalysis, is reported to enable regioselective arylation at their unactivated β-C(sp3)-H bond. Notably, the new strategy applicable secondary anilines N-PMP-protected primary aliphatic intermediate steric demands, which in contrast existing strategies that involve either free-amine-directed activation for highly sterically hindered or steric-controlled migrative cross-coupling unhindered N-Boc protected amines. Regioselectivity reaction imposed electronic effects imine intermediates rather than between specific starting materials catalysts, thereby opening uncharted scope In a broader sense, this study demonstrates opportunities involving hydrogen borrowing chemistry, previously explored alcohols, execute otherwise challenging transformations amines, commonly present natural products, pharmaceuticals, biologically active molecules, functional materials.

Language: Английский

Citations

1