Synthesis of Conjugated Polymers by Sustainable Suzuki Polycondensation in Water and under Aerobic Conditions DOI Creative Commons
Alessandro Sanzone,

Adiel Calascibetta,

Mauro Monti

et al.

ACS Macro Letters, Journal Year: 2020, Volume and Issue: 9(8), P. 1167 - 1171

Published: July 31, 2020

Conjugated semiconducting polymers are key materials enabling plastic (opto)electronic devices. Research in the field has a generally strong focus on constant improvement of backbone structure and resulting properties. Comparatively fewer studies devoted to improving sustainability synthetic route that leads material under scrutiny. Exemplified by two established commercially available luminescent poly(9,9-dioctylfluorene-alt-bithiophene) (PF8T2) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (PF8BT), this work describes first examples efficient Suzuki-Miyaura polycondensations water, ambient environment, with minimal amount organic solvent moderate heating. The approach enables reduction E-factor (mass waste/mass product) 1 order magnitude, without negatively affecting molecular weight, dispersity, chemical structure, or photochemical stability PF8T2 PF8BT.

Language: Английский

Water as the reaction medium in organic chemistry: from our worst enemy to our best friend DOI Creative Commons
Margery Cortes‐Clerget, Tzu‐Yu Yu, Joseph R. A. Kincaid

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(12), P. 4237 - 4266

Published: Jan. 1, 2021

A review presenting water as the logical reaction medium for future of organic chemistry. discussion is offered that covers both "on water" and "in phenomena, how playing unique roles in each, specifically with regard to its use synthesis.

Language: Английский

Citations

402
Emerging Trends in Cross-Coupling: Twelve-Electron-Based L1Pd(0) Catalysts, Their Mechanism of Action, and Selected Applications DOI Creative Commons
Sharbil J. Firsan,

Vilvanathan Sivakumar,

Thomas J. Colacot

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(23), P. 16983 - 17027

Published: Oct. 3, 2022

Monoligated palladium(0) species, L

Language: Английский

Citations

105
UV Light Generation and Challenging Photoreactions Enabled by Upconversion in Water DOI
Björn Pfund,

Debora M. Steffen,

Mirjam R. Schreier

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(23), P. 10468 - 10476

Published: May 15, 2020

Sensitized triplet–triplet annihilation (sTTA) is the most promising mechanism for pooling energy of two visible photons, but its applications in solution were so far limited to organic solvents, with a current maximum excited-singlet state 3.6 eV. By combining tailor-made iridium complexes naphthalenes, we demonstrate blue-light driven upconversion water unprecedented singlet-state energies approaching 4 The annihilators have outstanding excited-state reactivities enabling challenging photoreductions by sTTA. Specifically, found that an aryl-bromide bond activation can be achieved blue and obtained full conversion very energy-demanding decomposition persistent ammonium compound as typical pollutant, not only cw laser also LED light source. These results provide first proof-of-concept usage low-power sources reactions employing blue-to-UV pave way further development sustainable light-harvesting applications.

Language: Английский

Citations

106
Recent advances on micellar catalysis in water DOI
Tao Shen, Shaodong Zhou, Jiancheng Ruan

et al.

Advances in Colloid and Interface Science, Journal Year: 2020, Volume and Issue: 287, P. 102299 - 102299

Published: Oct. 26, 2020

Language: Английский

Citations

105
Pd-Catalyzed Cross-Couplings: On the Importance of the Catalyst Quantity Descriptors, mol % and ppm DOI Creative Commons
Christopher S. Horbaczewskyj, Ian J. S. Fairlamb

Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(8), P. 2240 - 2269

Published: July 11, 2022

This Review examines parts per million (ppm) palladium concentrations in catalytic cross-coupling reactions and their relationship with mole percentage (mol %). Most studies chemistry have historically focused on the concentration ratio between (pre)catalyst limiting reagent (substrate), expressed as mol %. Several recent papers outlined use of "ppm level" an alternative means describing reaction systems. led us to delve deeper into literature assess whether is a practically useful descriptor catalyst quantities palladium-catalyzed reactions. Indeed, we conjectured that many could, unknowingly, employed low levels" (pre)catalyst, generally, what would spread ppm look like across selection reported vast array literature. In few selected examples, examined other metal systems for comparison palladium.

Language: Английский

Citations

45
Palladium-catalyzed micellar cross-couplings: An outlook DOI Creative Commons
Tharique N. Ansari, Fabrice Gallou, Sachin Handa

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 488, P. 215158 - 215158

Published: May 2, 2023

Language: Английский

Citations

30
Surfactant Technology: With New Rules, Designing New Sequences Is Required! DOI
Daniel J. Lippincott, Evan B. Landstrom, Margery Cortes‐Clerget

et al.

Organic Process Research & Development, Journal Year: 2019, Volume and Issue: 24(5), P. 841 - 849

Published: Dec. 2, 2019

With a growing toolbox of surfactant-mediated chemistry in water and an increased number scaled-up transformations has come tremendous learning [for example, see: Lipshutz, B. H.; et al. The Hydrophobic Effect Applied to Organic Synthesis: Recent Synthetic Chemistry "in Water". Chem. - Eur. J. 2018, 24 (26), 6672–6695]. These opportunities now reside within few expert groups, while all the details are far from fully understood or still under development, substantial know-how been gained both reaction process synthesis design. Herein we share some fundamental principles inherent micellar catalysis illustrate them on particularly challenging case involving Suzuki–Miyaura cross-coupling. complete structures active pharmaceutical ingredient (API) intermediates not disclosed for confidentiality reasons but can nevertheless serve as illustrative importance factors that, unlike traditional organic solvents, be crucial successful outcome (e.g., lipophilicity). API used example this discussion bears significant commonality with large other targets associated formation biphenyl array well presence amide products resulting nucleophilic aromatic substitutions (SNAr). Hence, look utilize these prior learnings rapidly apply design optimal conditions several important transformations.

Language: Английский

Citations

56
Recent Applications of Pd-Catalyzed Suzuki–Miyaura and Buchwald–Hartwig Couplings in Pharmaceutical Process Chemistry DOI Creative Commons
Balaram S. Takale, Fanyi Kong,

Ruchita R. Thakore

et al.

Organics, Journal Year: 2022, Volume and Issue: 3(1), P. 1 - 21

Published: Jan. 18, 2022

Cross-coupling reactions have changed the way complex molecules are synthesized. In particular, Suzuki–Miyaura and Buchwald–Hartwig amination given opportunities to elegantly make pharmaceutical ingredients. Indeed, these at forefront of both stages drug development, medicinal chemistry, process chemistry. On one hand, chemists a resource derivatize core compound arrive scaffold rapidly. other cross couplings offered smart tool synthesize development candidates safely, quickly, efficiently. Generally, application cross-coupling is broad. This review will specifically focus on their real (pharma) world applications in large-scale synthesis appearing last three years.

Language: Английский

Citations

32
Selectivity in micellar catalysed reactions: The role of interfacial dipole, compartmentalisation, and specific interactions with the surfactants DOI Creative Commons
Sara Mattiello, Erika Ghiglietti, Anita Zucchi

et al.

Current Opinion in Colloid & Interface Science, Journal Year: 2023, Volume and Issue: 64, P. 101681 - 101681

Published: Feb. 13, 2023

Micellar catalysis is playing a major role in green chemistry with ever increasing applications the efficient and sustainable preparation of natural compounds, drugs, more recently organic semiconductors for printed electronics.Most contributions field focus on developments surfactants suitable formulative conditions capable reproducingand often improvingthe yield reactions commonly performed solvents.The real ambition micellar approach goes beyond improvement sustainability existing methods aims at mimicking not only efficiency but also selectivity enzymatic catalysis.This review summarizes relevant examples enabled, efficient, selective transformations, discusses different kind processes impacting product distribution depending details state achieved.

Language: Английский

Citations

19
N,C-Disubstituted Biarylpalladacycles as Precatalysts for ppm Pd-Catalyzed Cross Couplings in Water under Mild Conditions DOI

Ruchita R. Thakore,

Balaram S. Takale, Fabrice Gallou

et al.

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(12), P. 11647 - 11657

Published: Nov. 11, 2019

Various monosubstitution and disubstitution patterns on the parent biarylamine skeleton characteristic of palladacycles, as well counterion effect, have been studied while looking for ways to increase effectiveness catalyst formed under micellar catalysis conditions in water, with goal reducing amount Pd needed coupling reactions. Several substituted palladacycles containing readily accessible ligands were chosen evaluation. The results indicate that (1) preactivation Pd(II) salts precursors Suzuki–Miyaura (SM) couplings via treatment a agent is not required; (2) reactions could be performed approximately half loading Pd, relative previously required based combination salt ligand; (3) most effective palladacycle precatalyst has identified an isopropyl group both aryl ring nitrogen, together ligand EvanPhos triflate (P13). This also other C–C bond-forming reactions, such Heck Sonogashira couplings. No organic solvents these processes, aqueous reaction medium recycled several times. A one-pot, four-step sequence involving Suzuki–Miyaura, reduction, alkylation, acylation highlights potential this maximize synthetic gain minimizing costs waste generation.

Language: Английский

Citations

53