Mechanism-Guided Development of Transition-Metal-Catalyzed C–N Bond-Forming Reactions Using Dioxazolones as the Versatile Amidating Source DOI
Seung Youn Hong, Yeongyu Hwang, Minhan Lee

et al.

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(11), P. 2683 - 2700

Published: May 12, 2021

ConspectusCatalytic reactions that construct carbon–nitrogen bonds are one of central themes in both synthetic and medicinal chemistry since the obtainable nitrogen-containing motifs commonly encountered natural products have also seen a growing prominence as key structural features marketed drugs preclinical candidates. Pd-catalyzed cross-couplings, such Buchwald–Hartwig amination, at forefront methods practical settings. However, they require prefunctionalized substrates (hetero)aryl halides must be prepared independently, often by multiple operations. One emerging way to circumvent these preparatory steps directly convert ubiquitous C–H into valuable C–N is catalytic which allows chemists devise shorter more efficient retrosynthetic schemes. The past two decades witnessed considerable progress expanding repertoire this strategy, especially identifying effective amino group precursors. In context, dioxazolones experienced dramatic resurgence recent years versatile nitrogen source combination with transition-metal catalyst systems facilitate decarboxylation access metal-acylnitrenoid intermediates. addition their high robustness easy accessibility from abundant carboxylic acids, unique reactivity transient intermediates amido transfer has led fruitful journey for mild amidation reactions.This Account summarizes our contributions development bond-forming using nitrenoid precursors, categorized subsets according mechanistic differences: inner- versus outer-sphere pathways. first section describes how we could unveil potential realm inner-sphere amidation, where demonstrated serve not only manageable alternatives acyl azides but highly reagents significantly reduce loading temperature. Taking advantage conditions 9 Cp*M complexes (M = Rh, Ir, Co) or isoelectronic Ru species, dramatically expanded accessible scope. Mechanistic investigations revealed putative metal-nitrenoid species involved intermediate during catalysis, leads facile bond formation. On basis underpinning, succeeded developing novel platforms harness intermediacy metal-nitrenoids explore insertion via an pathway. Indeed, tailored catalysts were capable suppressing competitive Curtius-type decomposition, thus granting lactam products. We further repurposed upon modification chelating ligands identity transition metal achieve three goals: (i) addressing selectivity issues control regio-, chemo-, enantioselectivities, (ii) sustainable catalysis first-low metals, (iii) navigating chemical space (di)functionalization alkenes/alkynes. Together own research efforts, highlighted herein some important relevant advances other groups. finally conclude brief overview eye toward developments.

Language: Английский

3d Transition Metals for C–H Activation DOI
Parthasarathy Gandeepan, Thomas Müller, Daniel Zell

et al.

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

Citations

1966
Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications DOI
Yoonsu Park,

Youyoung Kim,

Sukbok Chang

et al.

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 9247 - 9301

Published: Jan. 4, 2017

Catalytic transformation of ubiquitous C-H bonds into valuable C-N offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven be a powerful tool for direct conversion cheap hydrocarbons synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular amination reactions utilizing late metal-based catalysts. Initial discovery, mechanistic study, additional applications were categorized on basis scaffolds types reactions. Reactivity selectivity novel systems are discussed three sections, with each being defined by proposed working mode.

Language: Английский

Citations

1921
Mild metal-catalyzed C–H activation: examples and concepts DOI Creative Commons
Tobias Gensch, Matthew N. Hopkinson, Frank Glorius

et al.

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(10), P. 2900 - 2936

Published: Jan. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

Language: Английский

Citations

1660
A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry DOI Creative Commons
Carlo Sambiagio, David Schönbauer, Rémi Blieck

et al.

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Language: Английский

Citations

1464
Cobalt-Catalyzed C–H Activation DOI

Marc Moselage,

Jie Li, Lutz Ackermann

et al.

ACS Catalysis, Journal Year: 2015, Volume and Issue: 6(2), P. 498 - 525

Published: Nov. 24, 2015

Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with development of cobalt-catalyzed functionalizations either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, progress field organometallic is reviewed until November 2015.

Language: Английский

Citations

1154
Catalytic Methods for Aromatic C–H Amination: An Ideal Strategy for Nitrogen-Based Functional Molecules DOI
Jiao Jiao, Kei Murakami, Kenichiro Itami

et al.

ACS Catalysis, Journal Year: 2015, Volume and Issue: 6(2), P. 610 - 633

Published: Dec. 7, 2015

Transformations of aromatic compounds into the corresponding amines, amides, and imides through carbon–hydrogen (C–H) bond functionalization represent one most step- atom-economical methods for synthesis arylamine compounds. Because arylamines are privileged structures in materials- biology-oriented functional molecules, development novel efficient synthetic C–H amination has received significant attention from a wide range research fields including materials pharmaceuticals. This review covers recent advances catalytic reactions. An array recently developed new reactions categorized by nature substrates: (1) 5-membered heteroarenes, (2) arenes having nitrogen moiety molecule (intramolecular amination), (3) directing group, (4) simple with excess amounts, (5) as limiting reagents.

Language: Английский

Citations

482
(Pentamethylcyclopentadienyl)cobalt(III)‐Catalyzed C–H Bond Functionalization: From Discovery to Unique Reactivity and Selectivity DOI
Tatsuhiko Yoshino, Shigeki Matsunaga

Advanced Synthesis & Catalysis, Journal Year: 2017, Volume and Issue: 359(8), P. 1245 - 1262

Published: March 16, 2017

Abstract High‐valent (pentamethylcyclopentadienyl)cobalt(III) [Cp*Co(III)] catalysts were found as inexpensive alternatives to (pentamethylcyclopentadienyl)rhodium(III) [Cp*Rh(III)] in the field of C—H bond functionalization, and applied a variety transformations. In this review, after discovery early examples Cp*Co(III)‐catalyzed functionalization are summarized, unique reactivity selectivity Cp*Co(III) differences between cobalt rhodium catalysis intensively discussed. Such assumed be caused by lower electronegativity, hard nature, smaller ionic radius cobalt. magnified image

Language: Английский

Citations

419
Transition metal-catalysed couplings between arenes and strained or reactive rings: combination of C–H activation and ring scission DOI
Fen Wang, Songjie Yu, Xingwei Li

et al.

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(23), P. 6462 - 6477

Published: Jan. 1, 2016

Transition metal-catalysed systems of C–H activation arenes in combination with opening strained or reactive three, four, and five membered rings are summarized this review.

Language: Английский

Citations

327
Catalytic Transformations of Functionalized Cyclic Organic Carbonates DOI
Wusheng Guo, José Enrique Gómez, Àlex Cristòfol

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(42), P. 13735 - 13747

Published: June 6, 2018

Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening decarboxylative catalytic transformations allowing the development of new stereo- enantioselective C-N, C-O, C-C, C-S C-B bond formation reactions. Transition-metal-mediated conversions only recently been rejuvenated powerful approaches towards preparation more complex molecules. This minireview will highlight potential structurally with a focus on their synthetic value mechanistic manifolds that are involved upon conversion.

Language: Английский

Citations

320
Cobalt(II)-Catalyzed Electrooxidative C–H Amination of Arenes with Alkylamines DOI
Xinlong Gao, Pan Wang, Li Zeng

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(12), P. 4195 - 4199

Published: March 9, 2018

An environmentally friendly electrochemical protocol about cobalt-catalyzed C–H amination of arenes has been developed, which offers a simple way to access synthetically useful arylamines. In divided cells, wide variety and alkylamines are examined afford C–N formation products without using external oxidants, avoids the undesired byproducts exhibits high atom economy. Importantly, reaction can also be extended gram level with moderate efficiency. KIE experiments indicate that bond cleavage might not involved during rate-limiting step.

Language: Английский

Citations

294