Renewable Solvents for Palladium-Catalyzed Carbonylation Reactions DOI Creative Commons
Aya Ismael, Ashot Gevorgyan, Troels Skrydstrup

et al.

Organic Process Research & Development, Journal Year: 2020, Volume and Issue: 24(11), P. 2665 - 2675

Published: Sept. 4, 2020

Solvents constitute the largest component for many chemical processes and substitution of nonrenewable solvents is a longstanding goal green chemistry. Here, we show that Pd-catalyzed carbonylative couplings, such as cross-couplings, aminocarbonylations, alkoxycarbonylations, can be successfully realized using renewable solvents. The present research covers not only well-established solvents, 2-methyltetrahydrofuran (2MeTHF), limonene, dimethyl carbonate, but also recently introduced biomass-derived 1,1-diethoxyethane, isosorbide ether, eucalyptol, rose oxide, γ-terpinene, α-pinene. coupling boronic acids aryl bromides works well in limonene. Aminocarbonylation gave excellent results α-pinene, while alkoxycarbonylation was successful 2MeTHF, carbonate. developed methods based on used synthesis commercial drug Trimetozine an analogue Itopride.

Language: Английский

C–H Activation: Toward Sustainability and Applications DOI Creative Commons
Toryn Dalton,

Teresa Faber,

Frank Glorius

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(2), P. 245 - 261

Published: Feb. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Language: Английский

Citations

575
Metalla-electrocatalyzed C–H Activation by Earth-Abundant 3d Metals and Beyond DOI
Lutz Ackermann

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(1), P. 84 - 104

Published: Dec. 19, 2019

To improve the efficacy of molecular syntheses, researchers wish to capitalize upon selective modification otherwise inert C-H bonds. The past two decades have witnessed considerable advances in coordination chemistry that set stage for transformative tools functionalizations. Particularly, oxidative C-H/C-H and C-H/Het-H transformations gained major attention because they avoid all elements substrate prefunctionalization. Despite advances, activations been dominated by precious transition metal catalysts based on palladium, ruthenium, iridium, rhodium, thus compromising sustainable nature overall activation approach. same holds true predominant use stoichiometric chemical oxidants regeneration active catalyst, prominently featuring hypervalent iodine(III), copper(II), silver(I) oxidants. Thereby, quantities undesired byproducts are generated, which preventive applications scale. In contrast, elegant merger homogeneous metal-catalyzed with electrosynthesis bears unique power achieve outstanding levels oxidant resource economy. Thus, contrast classical electrosyntheses control, metalla-electrocatalysis huge largely untapped potential unmet site selectivities means catalyst control. While indirect electrolysis using palladium complexes has realized, less toxic expensive base feature distinct beneficial assets toward this Account, I summarize emergence electrocatalyzed earth-abundant 3d metals beyond, a topical focus contributions from our laboratories through November 2019. cobalt electrocatalysis was identified as particularly powerful platform wealth transformations, including oxygenations nitrogenations well alkynes, alkenes, allenes, isocyanides, carbon monoxide, among others. As complementary tools, nickel, copper, very recently iron devised metalla-electrocatalyzed activations. Key success were detailed mechanistic insights, oxidation-induced reductive elimination scenarios. Likewise, development methods make weak O-coordination benefited crucial insights into catalyst's modes action experiment, operando spectroscopy, computation. Overall, thereby syntheses These electrooxidative frequently characterized improved chemoselectivities. Hence, ability dial redox at minimum level required desired transformation renders an ideal functionalization structurally complex molecules sensitive functional groups. This strategy was, inter alia, successfully applied scale-up continuous flow step-economical assembly polycyclic aromatic hydrocarbons.

Language: Английский

Citations

519
C–H activation DOI
Torben Rogge, Nikolaos Kaplaneris, Naoto Chatani

et al.

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

Citations

433
3d metallaelectrocatalysis for resource economical syntheses DOI Creative Commons
Parthasarathy Gandeepan, Lars H. Finger, Tjark H. Meyer

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4254 - 4272

Published: Jan. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Language: Английский

Citations

186
Replacement strategies for non-green dipolar aprotic solvents DOI
Feng Gao, Rongxian Bai, Francesco Ferlin

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(19), P. 6240 - 6257

Published: Jan. 1, 2020

Despite their wide use in many fields, common dipolar aprotic solvents are urged to be replaced because of detrimental effects on health and environment. Therefore, green replacement strategies synthesis have been summarized.

Language: Английский

Citations

159
Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives DOI Creative Commons
Andrew Jordan, Callum G. J. Hall,

Lee R. Thorp

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 6749 - 6794

Published: Feb. 24, 2022

Dipolar aprotic and ethereal solvents comprise just over 40% of all organic utilized in synthetic organic, medicinal, process chemistry. Unfortunately, many the common "go-to" are considered to be "less-preferable" for a number environmental, health, safety (EHS) reasons such as toxicity, mutagenicity, carcinogenicity, or practical handling flammability volatility. Recent legislative changes have initiated implementation restrictions on use commonly employed dipolar dimethylformamide (DMF) N-methyl-2-pyrrolidinone (NMP), ethers 1,4-dioxane. Thus, with growing legislative, EHS, societal pressures, need identify implement alternative that greener, safer, more sustainable has never been greater. Within this review, ubiquitous nature is discussed respect physicochemical properties made them so appealing chemists. An overview current being imposed discussed. A variety alternative, garnered attention past decade then examined, case studies examples where less-preferable successfully replaced safer highlighted. Finally, general guidance solvent selection replacement included Supporting Information review.

Language: Английский

Citations

111
Sustainable protocols for direct C–H bond arylation of (hetero)arenes DOI
Gianluigi Albano, Angela Punzi, Maria Annunziata M. Capozzi

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(5), P. 1809 - 1894

Published: Jan. 1, 2022

A comprehensive and critical overview of the sustainable strategies for direct C–H bond arylation (hetero)arenes, based on use recoverable catalysts, solvents non-conventional energy sources, has been performed.

Language: Английский

Citations

71
Solar reforming as an emerging technology for circular chemical industries DOI
Subhajit Bhattacharjee, Stuart Linley, Erwin Reisner

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(2), P. 87 - 105

Published: Jan. 30, 2024

Language: Английский

Citations

51
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
Renewable resources for sustainable metallaelectro-catalysed C–H activation DOI Creative Commons
Ramesh C. Samanta, Tjark H. Meyer, Inke Siewert

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(33), P. 8657 - 8670

Published: Jan. 1, 2020

The merger of C–H activation with electrosynthesis, powered by renewable energies and resources, will guide towards a sustainable future.

Language: Английский

Citations

84