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Scope and Limitation of Propylene Carbonate As a Sustainable Solvent in the Suzuki–Miyaura Cite This: RSC Adv.,2019,9,37818 Reaction†

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Scope and Limitation of Propylene Carbonate As a Sustainable Solvent in the Suzuki–Miyaura Cite This: RSC Adv.,2019,9,37818 Reaction† RSC Advances PAPER View Article Online View Journal | View Issue Scope and limitation of propylene carbonate as a sustainable solvent in the Suzuki–Miyaura Cite this: RSC Adv.,2019,9,37818 reaction† a a a b Andrea Czompa, Balazs´ Laszl´ oP´ asztor,´ Jennifer Alizadeh Sahar, Zoltan´ Mucsi, ac d e ac Dora´ Bogdan,´ Krisztina Ludanyi,´ Zoltan´ Varga and Istvan´ M. Mandity´ * The Suzuki–Miyaura reaction is one of the most used transformations in drug research. Thus making this reaction more sustainable is of considerable current interest. Here we show that propylene carbonate (PC) can be used as a solvent for the Suzuki–Miyaura reaction. PC is one of the greenest solvents since it is synthesized under green conditions by the use of carbon dioxide in the air. All reactions proceeded Received 3rd September 2019 well and good or excellent yields were observed for the biaryl products. Nonetheless in the case of Accepted 29th October 2019 pyridazinones, 2-hydroxypropyl- chain containing side-products were observed. Importantly, this fact DOI: 10.1039/c9ra07044c allowed the isolation of several novel compounds which were generated under prominently green Creative Commons Attribution 3.0 Unported Licence. rsc.li/rsc-advances conditions. Introduction propylene carbonate (PC) and various polar and nonpolar solvents on palladium-catalyzed Suzuki–Miyaura coupling of The Suzuki–Miyaura reaction is the palladium-catalysed cross- chloroaryl triates. They highlighted the similar selectivity of 21 coupling reaction of organoboranes with organic halides, tri- the solvents and the synthetic value of it. PC was used with no ates or peruorinated sulfonates and proceeds with high loss of enantioselectivity in an iridium- and rhodium- stereo- and regioselectivity.1 Recent developments with respect phosphite/oxazoline catalytic system catalysed asymmetric 22 This article is licensed under a to catalysts and methods have broadened the possible appli- hydrogenation of functionalized cyclic b-enamines, and in cations enormously, that is, the scope of the reaction partners is cathodic reduction of aryl halides, considered for its high 23 not restricted to aryls, but includes alkyls, alkenyls and alkynyls dielectric permittivity. PC was used in an aminophosphine too.2,3 Usually, the boronic acid is activated by a base and the palladium pincer-catalyzed carbonylative Sonogashira reaction Open Access Article. Published on 20 November 2019. Downloaded 10/1/2021 1:09:34 AM. À reaction is run in a polar aprotic solvent, ionic liquid or water.4 with 10 4 mol%, while the Suzuki–Miyaura cross-coupling À 24 At room temperature, the reaction takes place with low yield; reaction was carried out at 10 6 mol%. Nonetheless, Pd/C therefore, the use of special catalyst might be required5 or catalysed phenoxycarbonylation of aryl iodide was carried out increased temperature and pressure are needed.6 using N-formylsaccharin as a CO surrogate in PC as a sustain- 25 Several efforts were taken to carry out Suzuki–Miyaura and able solvent. Heck reaction was carried in cyclic carbonates as further cross coupling reactions under green and sustainable greener solvents, offering effective alternative to traditionally 26 conditions.7–20 Reeves and co-workers studied the effects of used dipolar aprotic solvents. Nanostructured palladium clusters catalysed also Heck reaction and were stable in propylene carbonate even at 140–155 C.27 28 aDepartment of Organic Chemistry, Faculty of Pharmacy, Semmelweis University, A recent article reports that nanoparticles formed from } Hogyes Endre u. 7, H-1092 Budapest, Hungary. E-mail: mandity.istvan@pharma. inexpensive FeCl3 naturally contains parts-per-million (ppm) semmelweis-univ.hu; [email protected] levels of Pd and can catalyse Suzuki–Miyaura reaction in water. b } Femtonics Ltd, Tuzolto´ u. 59, H-1094 Budapest, Hungary There is also a nickel-catalysed, but base-free Suzuki–Miyaura cMTA TTK Lendulet¨ Articial Transporter Research Group, Institute of Materials and reaction of carboxylic acid uorides29 and we can found Environmental Chemistry, Research Center for Natural Sciences, Hungarian – Academy of Sciences, Magyar Tudosok´ krt. 2, H-1117 Budapest, Hungary a heterogeneous and ligand-free Suzuki Miyaura reaction dDepartment of Pharmaceutics, Semmelweis University, Hogyes} Endre u. 7, H-1092 accomplished with the use of a palladium catalyst supported on 30 Budapest, Hungary a double-structure amphiphilic polymer composite. Interest- eInstitute of Materials and Environmental Chemistry, Research Center for Natural ingly, a heterogeneous single-atom palladium preparation Sciences, Hungarian Academy of Sciences, Magyar Tudosok´ krt. 2, H-1117 Budapest, anchored on exfoliated graphitic carbon nitride was used in Hungary a homogenous systems for Suzuki coupling.31 In 2018, † Electronic supplementary information (ESI) available: General experimental 32 set-up experimental procedures including characterization data, researchers from the P zer company published an article 1 13 chromatograms, Hand C NMR spectra. See DOI: 10.1039/c9ra07044c about the use of an automated ow-based synthesis platform, 37818 | RSC Adv.,2019,9,37818–37824 This journal is © The Royal Society of Chemistry 2019 View Article Online Paper RSC Advances that integrates both rapid nanomole-scale reaction screening in lithium–metal batteries was studied in order to explore the and micromole-scale synthesis in Suzuki–Miyaura coupling at next-generation high-energy lithium–sulfur and lithium–air elevated temperature. The continuous-ow technology was batteries.50 PC can increase optoelectronic properties, photo- utilized for several cross coupling reactions too.11,33–38 voltaic parameters and environmental stability of efficient Small and homogenous palladium particules (4–6 nm) were perovskite solar cells against humidity, light and heat.51 introduced in multi-walled carbon nanotubes used for selective Herein we show the use of PC as prominent green solvent for hydrogenation of cinnamaldehyde,39 while palladium–nickel the Suzuki–Miyaura reaction. We observed the limitation of PC and palladium–silver nanoparticles supported on carbon as solvent, since nucleophiles can open the ring and 2-hydrox- exhibited high activity toward the glycerol electrooxidation in ypropylation occurs. Nonetheless, this side-reaction allowed us alkaline medium.40 Glycerol electrooxidation was achieved also the isolation of several novel compounds, thus, PC can be on active self-supported Pd1Snx nanoparticles, when the modi- treated as a prominently green 2-hydroxypropylation reagent. cation of palladium by tin species led to suppress the disso- ciative adsorption process of glycerol.41 de Souza and co-workers published an article describing the resolution of amines.42 They Results and discussion immobilized lipase on functionalized Pd–SiO nanoparticles 2 As mentioned, two different heating ways (oil bath and MW and this new simplied Pd-lipase hybrid biocatalysts showed irradiation) were applied in the Suzuki–Miyaura reaction with 2- immobilization efficiencies of around 80% when containing 1– iodopyridine (2), 4-iodopyridine (3) and 6-iodopyridazin-3(2H)- 10% of Pd. Numerous studies focused on the bacterial synthesis one (4) as starting materials. The rst two are commercial of Pd-nanoparticles (bio-Pd NPs) by uptake of Pd(II) ions and products, while the last one was synthesized in two steps from their enzymatically-mediated reduction to Pd(0). One of them commercially available 3,6-dichloropyridazine. The chlorine deal with microwave-injured Pd(II)-treated cells (and non MW- 52,53 atoms were substituted with iodine in the presence of aq. HI treated controls) which were contacted with H2 to promote 43 followed by alkaline hydrolysis of the formed 3,6-diiodopyr- II 54,55 Creative Commons Attribution 3.0 Unported Licence. Pd( ) reduction. idazine in order to obtain 6-iodopyridazin-3(2H)-on (4). The The Suzuki–Miyaura reaction was investigated under tradi- heterocyclic substrates were reacted with four different boronic tional oil-heating and microwave conditions using propylene acids (Scheme 2), namely, 2-naphthylboronic acid (5), phenyl- carbonate (PC, 1, Scheme 1) as a green solvent. Three hetero- boronic acid (6), 4-biphenylboronic acid (7) and 4-uo- cyclic substrates: 2-iodopyridine (2), 4-iodopyridine (3) and 6- rophenylboronic acid (8). iodopyridazin-3(2H)-one (4), were used as coupling partners. Reactions were carried out in the presence of tetrakis(- The use of PC allows to increase the temperature of the triphenylphosphane)palladium(0) as catalyst and disodium Suzuki reaction (usually lower or around 100 C) and meantime, carbonate as base. The Suzuki–Miyaura reaction of 5 with decrease the reaction time. Propylene carbonate (1) is among iodopyridines is shown on Scheme 3, while with iodopyridazin- This article is licensed under a the green solvents44 in the GlaxoSmithKline solvent sustain- 3(2H)-one 4 is depicted on Scheme 4. ability guide. It is known as a carbon-dioxide neutral solvent45 and can be obtained from propylene oxide and carbon dioxide.46 The cycloaddition of CO2 and propylene oxide catalysed by NiO- Open Access Article. Published on 20 November 2019. Downloaded 10/1/2021 1:09:34 AM. modi ed TiO2 nanoparticles with tetrabutylammonium iodide used as co-catalyst, under solvent free conditions was achieved in excellent yield47 and the green synthesis of PC was also published.48 In this last paper, the authors used microwave in order to intensify the lipase catalysed transesterication
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