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

Cobaltaelectro-Catalyzed Oxidative C–H/N–H Activation with 1,3-Diynes by Electro-Removable Hydrazides DOI
Ruhuai Mei, Wenbo Ma,

Yin Zhang

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(16), P. 6534 - 6538

Published: July 31, 2019

An efficient electro-oxidative C–H/N–H activation with 1,3-diynes has been achieved a robust earth-abundant cobalt catalyst. The electrochemical C–H functionalization was accomplished ample scope and remarkable functional group compatibility in simple undivided cell. This protocol avoids the utilization of stoichiometric cost-intensive chemical oxidants activation, thus forming hydrogen as only byproduct.

Language: Английский

Citations

83

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

Ruthenium-catalyzed C–H bond functionalization in cascade and one-pot transformations DOI Creative Commons

Rafael Gramage‐Doria,

Christian Bruneau

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 428, P. 213602 - 213602

Published: Oct. 15, 2020

Language: Английский

Citations

74

Sustainable flow approaches to active pharmaceutical ingredients DOI
Francesco Ferlin,

Daniela Lanari,

Luigi Vaccaro

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(18), P. 5937 - 5955

Published: Jan. 1, 2020

This review summarizes the adoption of flow technology for synthesis a variety APIs in period 2015–2020. A major attention has been dedicated to compare batch and procedures by also comparing their sustainability.

Language: Английский

Citations

72

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

Quantitative Sustainability Assessment of Flow Chemistry–From Simple Metrics to Holistic Assessment DOI
Volker Hessel, Marc Escribà‐Gelonch, Jodie Bricout

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(29), P. 9508 - 9540

Published: July 12, 2021

Flow chemistry has changed chemical process designs toward intensification and is generally considered as green methodology. In this connection, perspective provides a more critical holistic view about the sustainability of flow by introducing both simple complex tools for environmental quantitative assessment on providing examples how they were used chemistry. The latter also shows what can add to make processes sustainable. With increasing complexity assessment, metrics, life cycle methodology, circular transition indicators are discussed. way, assessed first level reaction only then moving beyond. chemists very aware principles their metrics. Yet, hardly use circularity analysis not been made. When those assessments used, it usually done researchers with an ecology background. This aims opportunities that provide protecting our planet requires consideration. critically states each three types do limitations are.

Language: Английский

Citations

56

Extensive Screening of Green Solvents for Safe and Sustainable UiO-66 Synthesis DOI Creative Commons
Diletta Morelli Venturi,

Filippo Campana,

Fabio Marmottini

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2020, Volume and Issue: 8(46), P. 17154 - 17164

Published: Nov. 11, 2020

Zirconium based metal–organic framework UiO-66 is to date considered one of the benchmark compounds among stable MOFs, and it has attracted huge attention for its employment in many strategic applications. Large scale production industrial purposes requires use safe green solvents, fulfilling chemistry principles able replace N,N-dimethylformamide (DMF), which, despite toxicity, still most efficient solvent obtaining high quality. Herein we report on a survey about 40 different solvents with polarities, boiling points acidities, used laboratory synthesis quality crystals. The were chosen according European REACH Regulation 1907/2006 those having low cost toxicity being fully biodegradable. Concerning MOF synthesis, relevant parameters establishing results obtained are degree crystallinity, microporosity, specific surface area, yield, recyclability. Taking into account also chemical physical properties all color code was assigned order give final assessment synthesis. Defectivity products, acidic modulators, alternative Zr salts have been taken consideration. Preliminary lead conclusion that GVL (γ-valerolactone) promising replacing DMF

Language: Английский

Citations

64

Cobalta-Electrocatalyzed C–H Allylation with Unactivated Alkenes DOI
Uttam Dhawa, Cong Tian, Weizhao Li

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(11), P. 6457 - 6462

Published: May 12, 2020

Versatile and robust cobalt catalysis enabled the electrochemical C–H allylation with nonactivated alkenes. In contrast to precious palladium, rhodium, iridium, ruthenium catalysts that are limited electronically activated styrenes acrylates, we herein disclose cobalt-catalyzed electro-oxidative allylations Thus, allylated benzamides were obtained high levels of chemoselectivity, positional selectivity, regioselectivity in biomass-derived solvent γ-valerolactone. Detailed mechanistic studies provided strong support for a base-assisted internal electrophilic-type substitution mechanism key activation step. The cobaltaelectro-catalysis overall achieved resource-economy by avoiding use stoichiometric chemical oxidants, H2 as only byproduct.

Language: Английский

Citations

60

Allenes for Versatile Iron-Catalyzed C–H Activation by Weak O-Coordination: Mechanistic Insights by Kinetics, Intermediate Isolation, and Computation DOI
Antonis M. Messinis, Lars H. Finger, Lianrui Hu

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(30), P. 13102 - 13111

Published: June 13, 2020

The iron-catalyzed hydroarylation of allenes was accomplished by weak phenone assistance. C-H activation proceeded with excellent efficacy and high ortho-regioselectivity in proximity to the weakly coordinating carbonyl group for a range substituted phenones allenes. Detailed mechanistic studies, including isolation key intermediates, structural characterization an iron-metallacycle, kinetic analysis, allowed sound elucidation plausible catalytic working mode. This rationale is supported detailed computational density functional theory which fully address multi-spin-state reactivity. Furthermore, operando nuclear magnetic resonance monitoring reaction provided insights into mode action alkylation

Language: Английский

Citations

59

Iron‐Electrocatalyzed C−H Arylations: Mechanistic Insights into Oxidation‐Induced Reductive Elimination for Ferraelectrocatalysis DOI Creative Commons
Cuiju Zhu, Maximilian Stangier, João C. A. Oliveira

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(71), P. 16382 - 16389

Published: Oct. 28, 2019

Despite major advances, organometallic C-H transformations are dominated by precious 5d and 4d transition metals, such as iridium, palladium rhodium. In contrast, the unique potential of less toxic Earth-abundant 3d metals has been underexplored. While iron is most naturally abundant metal, its use in oxidative, activation faced limitations due to need for superstoichiometric amounts corrosive, cost-intensive DCIB sacrificial oxidant. To fully address these restrictions, we describe herein unprecedented merger electrosynthesis with iron-catalyzed through oxidation-induced reductive elimination. Thus, ferra- manganaelectro-catalyzed arylations were accomplished at mild reaction temperatures ample scope action sustainable catalysts, employing electricity a benign

Language: Английский

Citations

55