Room-Temperature Synthesis of Isoindolone Spirosuccinimides: Merger of Visible-Light Photocatalysis and Cobalt-Catalyzed C–H Activation DOI
Chiranjit Sen,

Bhavesh Sarvaiya,

Souvik Sarkar

et al.

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(23), P. 15287 - 15304

Published: Nov. 3, 2020

A room-temperature C–H bond functionalization of benzamides has been developed by merging a photocatalyst with cobalt catalyst for the synthesis isoindolone spirosuccinimides. The reaction proceeds in aerobic conditions and does not require any sacrificial external oxidants such as Ag(I) or Mn(III) salts. Visible light activates photocatalyst, it acts an electron-transfer reagent helps fundamental organometallic steps modulating oxidation state complex. This spirocyclization showed wide substrate scope good functional group tolerance. possible mechanism was proposed from experimental outcome, showing that activation is irreversible rate-determining step.

Language: Английский

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration DOI Creative Commons
Luca Capaldo, Davide Ravelli, Maurizio Fagnoni

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Language: Английский

Citations

809
Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp3)–H Bonds DOI
Bin Liu, Andrew M. Romine, Camille Rubel

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

Citations

367
Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts DOI
Cong Ma, Ping Fang,

Zhao‐Ran Liu

et al.

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

Citations

293
Cobalt-Catalyzed Enantioselective C–H Annulation with Alkenes DOI
Dandan Yang, Xian Zhang, Xinghua Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4250 - 4260

Published: March 13, 2023

Herein, we disclose an efficient cobalt-catalyzed enantioselective C–H activation and annulation of benzamides with alkenes. This transformation is facilitated via the commercially available cobalt(II) catalyst in presence easily prepared chiral salicyl-oxazoline (Salox) ligand, which provides facile access to (R) or (S) enantiomers dihydroisoquinolone derivatives. It noticeable that reaction proceeded efficiently within extremely short time from 10 30 min under mild conditions. A broad range alkenes bear various functional substituents have been shown good compatibility deliver targeted products high yields enantioselectivities (51 examples, up 98% yield 99% ee). The gram scale experiment removal directing group further demonstrate practicability this protocol potential industrial applications. Density theory calculations elucidate mechanism, spin-state change olefin insertion step accelerates subsequent C–N reductive elimination, identified as stereo-determining step. AIM analysis indicates π interactions are vital for controlling switching stereoselectivity.

Language: Английский

Citations

45
Cobalt‐Catalyzed Oxidative C−H Activation: Strategies and Concepts DOI
Ruhuai Mei, Uttam Dhawa, Ramesh C. Samanta

et al.

ChemSusChem, Journal Year: 2020, Volume and Issue: 13(13), P. 3306 - 3356

Published: Feb. 17, 2020

Inexpensive cobalt-catalyzed oxidative C-H functionalization has emerged as a powerful tool for the construction of C-C and C-Het bonds, which offers unique potential transformative applications to modern organic synthesis. In early stage, these transformations typically required stoichiometric toxic transition metals sacrificial oxidants; thus, formation metal-containing waste was inevitable. contrast, naturally abundant molecular O2 more recently been successfully employed green oxidant in cobalt catalysis, thus considerably improving sustainability such transformations. Recently, significant momentum gained by use electricity sustainable environmentally benign redox reagent functionalization, thereby preventing consumption cost-intensive chemicals while at same time addressing considerable safety hazards related oxygen combination with flammable solvents. Considering unparalleled aforementioned approaches synthesis, this Review summarizes recent progress activation until 2020.

Language: Английский

Citations

95
Catalytic addition of C–H bonds across C–C unsaturated systems promoted by iridium(i) and its group IX congeners DOI Creative Commons
David F. Fernández, José L. Mascareñas, Fernando López

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(20), P. 7378 - 7405

Published: Jan. 1, 2020

Transition metal-catalyzed hydrocarbonations of unsaturated substrates have emerged as powerful synthetic tools for increasing molecular complexity in an atom-economical manner. Although this field was traditionally dominated by low valent rhodium and ruthenium catalysts, recent years, there been many reports based on the use iridium complexes. In cases, these reactions a different course from those their homologs, even allow performing otherwise inviable transformations. review we aim to provide informative journey, early pioneering examples field, most them other metals than iridium, transformations catalyzed designed Ir(i) The is organized type C-H bond that activated (with C sp2, sp or sp3), well C-C partner used hydrocarbonation (alkyne, allene alkene). Importantly, discuss mechanistic foundations methods highlighting differences previously proposed processes related metals, particularly same group (Co Rh).

Language: Английский

Citations

93
Green strategies for transition metal-catalyzed C–H activation in molecular syntheses DOI Creative Commons
Uttam Dhawa, Nikolaos Kaplaneris, Lutz Ackermann

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(17), P. 4886 - 4913

Published: Jan. 1, 2021

Sustainable strategies for the activation of inert C–H bonds towards improved resource-economy.

Language: Английский

Citations

81
Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect DOI
Ishani Borthakur,

Anirban Sau,

Sabuj Kundu

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

Language: Английский

Citations

77
Transition Metal Promoted Cascade Heterocycle Synthesis through C−H Functionalization DOI

Alessio Baccalini,

Giuseppe Faita,

Giuseppe Zanoni

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(44), P. 9749 - 9783

Published: June 18, 2020

Sequential, domino and tandem reactions could be defined as a sequence of synthetic transformations that occur one after the other, in same reaction flask. This Review highlights recent advances at overlap two worlds: transition-metal mediated C-H activation trigger cascade reaction, for heterocycles synthesis. To shed some light on this intricate "middle-earth", focus was put mechanism rather than type metal or chronological order reaction. The aim is to separate, then highlight, true initiated by activation, compared other examples functionalization heterocycle syntheses.

Language: Английский

Citations

76
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

68