Special Issue "Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: closed (30 November 2016)

Special Issue Editor

Guest Editor
Dr. Ioannis D. Kostas

National Hellenic Research Foundation, Institute of Biology, Medicinal Chemistry and Biotechnology, Vas. Contantinou 48, 11635 Athens, Greece
Website | E-Mail
Interests: transition metal homogeneous catalysis in organic synthesis; catalysis by metal nanoparticles; medicinal chemistry

Special Issue Information

Dear Colleagues,

Suzuki–Miyaura cross-coupling remains a powerful tool in organic synthesis for C–C bond formation and has various industrial applications, such as for the synthesis of pharmaceuticals and materials. Intensive research efforts are being made into finding ways of improving and expanding the scope of this process, and the development of more efficient catalytic systems for this extremely important reaction is still a hot research topic of enormous academic and industrial interest.

This Special Issue aims to cover promising research and novel trends in the broad field of Suzuki–Miyaura cross-coupling, employing a range of different catalysts. Catalysis may be homogeneous or heterogeneous, and the transformations may be in mono- or biphasic systems, using conventional conditions or by application of non-conventional techniques (e.g. ultrasound, microwaves). The catalysts may be supported or unsupported metal complexes with phosphane- or phosphane-free ligands, as well as metal nanoparticles. Studies on catalyst recycling, coupling of non-activated substrates, mechanistic insights, and also potential applications for the synthesis of fine chemicals and intermediates used in the manufacture of drugs and materials would also be of great interest.

Dr. Ioannis D. Kostas
Guest Editor

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Cross-coupling
  • C-C bond formation
  • Noble metals
  • Homogeneous catalysis
  • Metal complex
  • Phosphane ligand
  • Phosphane-free ligand
  • Multiphase catalysis
  • Heterogeneous catalysis
  • Metal nanoparticles

Published Papers (12 papers)

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Research

Jump to: Review

Open AccessCommunication Intramolecular Transfer of Pd Catalyst on Carbon–Carbon Triple Bond and Nitrogen–Nitrogen Double Bond in Suzuki–Miyaura Coupling Reaction
Catalysts 2017, 7(7), 195; doi:10.3390/catal7070195
Received: 24 March 2017 / Revised: 19 June 2017 / Accepted: 20 June 2017 / Published: 23 June 2017
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Abstract
Intramolecular transfer of t-Bu3P-ligated Pd catalyst on a carbon–carbon triple bond (C≡C) and nitrogen–nitrogen double bond (N=N) was investigated and compared with the case of a carbon–carbon double bond (C=C), which is resistant to intramolecular transfer of the Pd catalyst.
[...] Read more.
Intramolecular transfer of t-Bu3P-ligated Pd catalyst on a carbon–carbon triple bond (C≡C) and nitrogen–nitrogen double bond (N=N) was investigated and compared with the case of a carbon–carbon double bond (C=C), which is resistant to intramolecular transfer of the Pd catalyst. Suzuki–Miyaura coupling reaction of equimolar 4,4’-dibromotolan (1a) or 4,4’-dibromoazobenzene (1b) with 3-isobutoxyphenylboronic acid (2) was carried out in the presence of t-Bu3P-ligated Pd precatalyst 3 and KOH/18-crown-6 as a base at room temperature. In both cases, the diphenyl-substituted product was selectively obtained, indicating that the Pd catalyst walked from one benzene ring to the other through the C≡C or N=N bond after the first substitution with 2. Taking advantage of this finding, we conducted unstoichiometric Suzuki–Miyaura polycondensation of 1.3 equiv. of 1 and 1.0 equiv. of phenylenediboronic acid (ester) 6 in the presence of 3 and CsF/18-crown-6 as a base, obtaining high-molecular-weight conjugated polymer with a boronic acid (ester) moiety at both ends, contrary to the Flory principle. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessArticle Synthesis, Structural Characterization and Catalytic Evaluation of Anionic Phosphinoferrocene Amidosulfonate Ligands
Catalysts 2017, 7(6), 167; doi:10.3390/catal7060167
Received: 20 April 2017 / Revised: 19 May 2017 / Accepted: 19 May 2017 / Published: 24 May 2017
Cited by 1 | PDF Full-text (4425 KB) | HTML Full-text | XML Full-text
Abstract
Triethylammonium salts of phosphinoferrocene amidosulfonates with electron-rich dialkyphosphino substituents, R2PfcCONHCH2SO3(HNEt3) (4ac), where fc = ferrocene-1,1′-diyl, and R = i-Pr (a), cyclohexyl (Cy; b), and t-butyl (
[...] Read more.
Triethylammonium salts of phosphinoferrocene amidosulfonates with electron-rich dialkyphosphino substituents, R2PfcCONHCH2SO3(HNEt3) (4ac), where fc = ferrocene-1,1′-diyl, and R = i-Pr (a), cyclohexyl (Cy; b), and t-butyl (c), were synthesized from the corresponding phosphinocarboxylic acids-borane adducts, R2PfcCO2H·BH3 (1ac), via esters R2PfcCO2C6F5·BH3 (2ac) and adducts R2PfcCONHCH2SO3(HNEt3)·BH3 (3ac). Compound 4b was shown to react with [Pd(μ-Cl)(η-C3H5)]2 and AgClO4 to afford the zwitterionic complex [Pd(η3-C3H5)(Cy2PfcCONHCH2SO32O,P)] (5b), in which the amidosulfonate ligand coordinates as a chelating donor making use of its phosphine moiety and amide oxygen. The structures of 3b·CH2Cl2, 4b and 5b·CH2Cl2 were determined by single-crystal X-ray diffraction analysis. Compounds 4ac and their known diphenylphosphino analogue, Ph2PfcCONHCH2SO3(HNEt3) (4d), were studied as supporting ligands in Pd-catalyzed cyanation of aryl bromides with K4[Fe(CN)6] and in Suzuki–Miyaura biaryl cross-coupling performed in aqueous reaction media under mild reaction conditions. In the former reaction, the best results were achieved with a catalyst generated from [PdCl2(cod)] (cod = η22-cycloocta-1,5-diene) and 2 equiv. of the least electron-rich ligand 4d in dioxane–water as a solvent. In contrast, the biaryl coupling was advantageously performed with a catalyst resulting from palladium(II) acetate and ligand 4a (1 equiv.) in the same solvent. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessArticle Graphene Oxide-Supported Oxime Palladacycles as Efficient Catalysts for the Suzuki–Miyaura Cross-Coupling Reaction of Aryl Bromides at Room Temperature under Aqueous Conditions
Catalysts 2017, 7(3), 94; doi:10.3390/catal7030094
Received: 25 January 2017 / Revised: 13 February 2017 / Accepted: 16 March 2017 / Published: 22 March 2017
Cited by 3 | PDF Full-text (5651 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Palladacycles are highly efficient precatalysts in cross-coupling reactions whose immobilization on carbonaceous materials has been hardly studied. Herein, we report a detailed study on the synthesis and characterization of new oxime palladacycle-graphene oxide non-covalent materials along with their catalytic activity in the Suzuki–Miyaura
[...] Read more.
Palladacycles are highly efficient precatalysts in cross-coupling reactions whose immobilization on carbonaceous materials has been hardly studied. Herein, we report a detailed study on the synthesis and characterization of new oxime palladacycle-graphene oxide non-covalent materials along with their catalytic activity in the Suzuki–Miyaura reaction. Catalyst 1-GO, which has been fully characterized by ICP, XPS, TGA, and UV-Vis analyses has been demonstrated to be an efficient catalyst for the Suzuki–Miyaura coupling between aryl bromides and arylboronic acids using very low catalyst loadings (0.002 mol % of Pd) at room temperature under aqueous conditions. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessFeature PaperArticle Suzuki-Miyaura C-C Coupling Reactions Catalyzed by Supported Pd Nanoparticles for the Preparation of Fluorinated Biphenyl Derivatives
Catalysts 2017, 7(3), 76; doi:10.3390/catal7030076
Received: 20 December 2016 / Revised: 23 February 2017 / Accepted: 24 February 2017 / Published: 28 February 2017
Cited by 2 | PDF Full-text (6867 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Heterogeneous recyclable catalysts in Suzuki-Miyaura C-C coupling reactions are of great interest in green chemistry as reusable alternatives to homogeneous Pd complexes. Considering the interesting properties of fluorinated compounds for the pharmaceutical industry, as precursors of novel materials, and also as components of
[...] Read more.
Heterogeneous recyclable catalysts in Suzuki-Miyaura C-C coupling reactions are of great interest in green chemistry as reusable alternatives to homogeneous Pd complexes. Considering the interesting properties of fluorinated compounds for the pharmaceutical industry, as precursors of novel materials, and also as components of liquid crystalline media, this present study describes the preparation of different fluorinated biphenyl derivatives by Suzuki-Miyaura coupling reactions catalyzed by a heterogeneous system (G-COOH-Pd-10) based on Pd nanoparticles supported onto COOH-modified graphene. The catalytic activity of the hybrid material G-COOH-Pd-10 has been tested in Suzuki-Miyaura C–C coupling reactions observing excellent versatility and good conversion rates in the reactions of phenylboronic acid, 4-vinylphenylboronic acid, 4-carboxyphenylboronic acid, and 4-fluorophenylboronic acid with 1-bromo-4-fluorobenzene. In addition, the influence of the arylbromide has been studied by carrying out reactions of 4-fluorophenylboronic acid with 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluorobenzene, 2-bromo-5-fluorotoluene, and 2-bromo-4-fluorotoluene. Finally, catalyst recyclability tests show a good degree of reusability of the system based on G-COOH-Pd-10 as the decrease in catalytic activity after five consecutive catalytic cycles in the reaction of 1-bromo-4-fluorobenzene with 4-florophenylboronic acid at 48 hours of reaction is lower than 8% while in the case of reactions at three hours the recyclability of the systems is much lower. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessCommunication Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues
Catalysts 2017, 7(1), 27; doi:10.3390/catal7010027
Received: 29 November 2016 / Revised: 4 January 2017 / Accepted: 10 January 2017 / Published: 13 January 2017
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Abstract
The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by
[...] Read more.
The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 °C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessArticle Plant Extract Mediated Eco-Friendly Synthesis of Pd@Graphene Nanocatalyst: An Efficient and Reusable Catalyst for the Suzuki-Miyaura Coupling
Catalysts 2017, 7(1), 20; doi:10.3390/catal7010020
Received: 27 November 2016 / Revised: 4 January 2017 / Accepted: 5 January 2017 / Published: 9 January 2017
Cited by 1 | PDF Full-text (4156 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Suzuki-Miyaura coupling reaction catalyzed by the palladium (Pd)-based nanomaterials is one of the most versatile methods for the preparation of biaryls. However, use of organic solvents as reaction medium causes a big threat to environment due to the generation of toxic byproducts as
[...] Read more.
Suzuki-Miyaura coupling reaction catalyzed by the palladium (Pd)-based nanomaterials is one of the most versatile methods for the preparation of biaryls. However, use of organic solvents as reaction medium causes a big threat to environment due to the generation of toxic byproducts as waste during the work up of these reactions. Therefore, the use of water as reaction media has attracted tremendous attention due to its environmental, economic, and safety benefits. In this study, we report on the synthesis of green Pd@graphene nanocatalyst based on an in situ functionalization approach which exhibited excellent catalytic activity towards the Suzuki–Miyaura cross-coupling reactions of phenyl halides with phenyl boronic acids under facile conditions in water. The green and environmentally friendly synthesis of Pd@graphene nanocatalyst (PG-HRG-Pd) is carried out by simultaneous reduction of graphene oxide (GRO) and PdCl2 using Pulicaria glutinosa extract (PGE) as reducing and stabilizing agent. The phytomolecules present in the plant extract (PE) not only facilitated the reduction of PdCl2, but also helped to stabilize the surface of PG-HRG-Pd nanocatalyst, which significantly enhanced the dispersibility of nanocatalyst in water. The identification of PG-HRG-Pd was established by various spectroscopic and microscopic techniques, including, high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), ultraviolet–visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy. The as-prepared PG-HRG-Pd nanocatalyst demonstrated excellent catalytic activity towards the Suzuki-Miyaura cross coupling reactions under aqueous, ligand free, and aerobic conditions. Apart from this the reusability of the catalyst was also evaluated and the catalyst yielded excellent results upon reuse for several times with marginal loss of its catalytic performance. Therefore, the method developed for the green synthesis of PG-HRG-Pd nanocatalyst and the eco-friendly protocol used for the Suzuki coupling offers a mild and effective substitute to the existing protocols and may significantly contribute to the endeavors of green chemistry. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessArticle Preparation of Pd-Diimine@SBA-15 and Its Catalytic Performance for the Suzuki Coupling Reaction
Catalysts 2016, 6(12), 181; doi:10.3390/catal6120181
Received: 1 October 2016 / Revised: 17 November 2016 / Accepted: 17 November 2016 / Published: 24 November 2016
Cited by 2 | PDF Full-text (7301 KB) | HTML Full-text | XML Full-text
Abstract
A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent
[...] Read more.
A highly efficient and stable Pd-diimine@SBA-15 catalyst was successfully prepared by immobilizing Pd onto diimine-functionalized mesoporous silica SBA-15. With the help of diimine functional groups grafted onto the SBA-15, Pd could be anchored on a support with high dispersion. Pd-diimine@SBA-15 catalyst exhibited excellent catalytic performance for the Suzuki coupling reaction of electronically diverse aryl halides and phenylboronic acid under mild conditions with an ultralow amount of Pd (0.05 mol % Pd). When the catalyst amount was increased, it could catalyze the coupling reaction of chlorinated aromatics with phenylboronic acid. Compared with the catalytic performances of Pd/SBA-15 and Pd-diimine@SiO2 catalysts, the Pd-diimine@SBA-15 catalyst exhibited higher hydrothermal stability and could be repeatedly used four times without a significant decrease of its catalytic activity. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessArticle Palladium Nanoparticles Tethered in Amine-Functionalized Hypercrosslinked Organic Tubes as an Efficient Catalyst for Suzuki Coupling in Water
Catalysts 2016, 6(10), 161; doi:10.3390/catal6100161
Received: 7 September 2016 / Revised: 14 October 2016 / Accepted: 14 October 2016 / Published: 20 October 2016
Cited by 5 | PDF Full-text (4197 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
It is highly desirable to design functionalized supports in heterogeneous catalysis regarding the stabilization of active sites. Pd immobilization in porous polymers and henceforth its application is a rapidly growing field. In virtue of its’ scalable synthesis and high stability in reaction conditions,
[...] Read more.
It is highly desirable to design functionalized supports in heterogeneous catalysis regarding the stabilization of active sites. Pd immobilization in porous polymers and henceforth its application is a rapidly growing field. In virtue of its’ scalable synthesis and high stability in reaction conditions, amorphous polymers are considered an excellent scaffold for metal mediated catalysis, but the majority of them are found as either agglomerated particles or composed of rough spheres. Owing to several important applications of hollow organic tubes in diverse research areas, we aimed to utilize them as support for the immobilization of Pd nanoparticles. Pd immobilization in nanoporous polymer tubes shows high activity in Suzuki cross coupling reactions between aryl halides and sodium phenyl trihydroxyborate in water, which deserves environmental merit. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Review

Jump to: Research

Open AccessFeature PaperReview Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling in Continuous Flow
Catalysts 2017, 7(5), 146; doi:10.3390/catal7050146
Received: 15 March 2017 / Revised: 18 April 2017 / Accepted: 25 April 2017 / Published: 9 May 2017
Cited by 1 | PDF Full-text (5537 KB) | HTML Full-text | XML Full-text
Abstract
Carbon–carbon cross-coupling reactions are among the most important processes in organic chemistry and Suzuki–Miyaura reactions are the most widely used protocols. For a decade, green chemistry and particularly catalysis and continuous flow, have shown immense potential in achieving the goals of “greener synthesis”.
[...] Read more.
Carbon–carbon cross-coupling reactions are among the most important processes in organic chemistry and Suzuki–Miyaura reactions are the most widely used protocols. For a decade, green chemistry and particularly catalysis and continuous flow, have shown immense potential in achieving the goals of “greener synthesis”. To date, it seems difficult to conceive the chemistry of the 21st century without the industrialization of continuous flow process in the area of pharmaceuticals, drugs, agrochemicals, polymers, etc. A large variety of palladium Suzuki–Miyaura cross-coupling reactions have been developed using a continuous flow sequence for preparing the desired biaryl derivatives. Our objective is to focus this review on the continuous flow Suzuki–Miyaura cross-coupling using homogeneous and heterogeneous catalysts. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessReview Eco-Friendly Physical Activation Methods for Suzuki–Miyaura Reactions
Catalysts 2017, 7(4), 98; doi:10.3390/catal7040098
Received: 31 December 2016 / Revised: 9 March 2017 / Accepted: 16 March 2017 / Published: 23 March 2017
Cited by 1 | PDF Full-text (32185 KB) | HTML Full-text | XML Full-text
Abstract
Eco-compatible activation methods in Suzuki–Miyaura cross-coupling reactions offer challenging opportunities for the design of clean and efficient synthetic processes. The main enabling technologies described in the literature are microwaves, ultrasound, grinding (mechanochemistry) and light. These methods can be performed in water or other
[...] Read more.
Eco-compatible activation methods in Suzuki–Miyaura cross-coupling reactions offer challenging opportunities for the design of clean and efficient synthetic processes. The main enabling technologies described in the literature are microwaves, ultrasound, grinding (mechanochemistry) and light. These methods can be performed in water or other green solvents with phase-transfer catalysis or even in solventless conditions. In this review, the authors will summarize the progress in this field mainly from 2010 up to the present day. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessReview The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization
Catalysts 2017, 7(3), 74; doi:10.3390/catal7030074
Received: 25 January 2017 / Revised: 20 February 2017 / Accepted: 21 February 2017 / Published: 25 February 2017
PDF Full-text (3860 KB) | HTML Full-text | XML Full-text
Abstract
The (site-selective) derivatization of amino acids and peptides represents an attractive field with potential applications in the establishment of structure–activity relationships and labeling of bioactive compounds. In this respect, bioorthogonal cross-coupling reactions provide valuable means for ready access to peptide analogues with diversified
[...] Read more.
The (site-selective) derivatization of amino acids and peptides represents an attractive field with potential applications in the establishment of structure–activity relationships and labeling of bioactive compounds. In this respect, bioorthogonal cross-coupling reactions provide valuable means for ready access to peptide analogues with diversified structure and function. Due to the complex and chiral nature of peptides, mild reaction conditions are preferred; hence, a suitable cross-coupling reaction is required for the chemical modification of these challenging substrates. The Suzuki reaction, involving organoboron species, is appropriate given the stability and environmentally benign nature of these reactants and their amenability to be applied in (partial) aqueous reaction conditions, an expected requirement upon the derivatization of peptides. Concerning the halogenated reaction partner, residues bearing halogen moieties can either be introduced directly as halogenated amino acids during solid-phase peptide synthesis (SPPS) or genetically encoded into larger proteins. A reversed approach building in boron in the peptidic backbone is also possible. Furthermore, based on this complementarity, cyclic peptides can be prepared by halogenation, and borylation of two amino acid side chains present within the same peptidic substrate. Here, the Suzuki–Miyaura reaction is a tool to induce the desired cyclization. In this review, we discuss diverse amino acid and peptide-based applications explored by means of this extremely versatile cross-coupling reaction. With the advent of peptide-based drugs, versatile bioorthogonal conversions on these substrates have become highly valuable. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Open AccessReview The Use of Palladium on Magnetic Support as Catalyst for Suzuki–Miyaura Cross-Coupling Reactions
Catalysts 2017, 7(1), 35; doi:10.3390/catal7010035
Received: 6 December 2016 / Revised: 17 January 2017 / Accepted: 19 January 2017 / Published: 23 January 2017
Cited by 7 | PDF Full-text (1498 KB) | HTML Full-text | XML Full-text
Abstract
The development of new solid supports for palladium has received a lot of interest lately. These catalysts have been tested in a range of cross-coupling reactions, such as Suzuki–Miyaura, Mizoroki-Heck, and Sonogashira cross-coupling reactions, with good outcomes. Attaching the catalyst to a solid
[...] Read more.
The development of new solid supports for palladium has received a lot of interest lately. These catalysts have been tested in a range of cross-coupling reactions, such as Suzuki–Miyaura, Mizoroki-Heck, and Sonogashira cross-coupling reactions, with good outcomes. Attaching the catalyst to a solid support simplifies the operations required in order to isolate and recycle the catalyst after a reaction has completed. Palladium on solid supports made of magnetic materials is particularly interesting since such catalysts can be removed very simply by utilizing an external magnet, which withholds the catalyst in the reaction vessel. This review will showcase some of the latest magnetic solid supports for palladium and highlight these catalysts’ performance in Suzuki–Miyaura cross-coupling reactions. Full article
(This article belongs to the Special Issue Suzuki–Miyaura Cross-Coupling Reaction and Potential Applications)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Electrophiles in Suzuki–Miyaura Cross-Coupling: More than Organohalides
Authors:
Kai Cheng
Short Abstract: Organohalides are extensively used as the coupling partners in Suzuki–Miyaura cross-coupling via C-X cleavage due to their relatively availablity. Much effort has been directed to search for alternative electrophiles to organohalides in these years Among them, N-based coupling partners (aryl diazonium salts, arylhydrazines), C-based coupling partners (arylcarboxylic acids), S-based coupling partners (aryl sulfonyl compounds), and O-based leaving groups (aryl ethers, carboxylates and sulfonates) have been well-documented. Recent progress for the research of alternative electrophiles will be described in this review.

Title: Aziridine- and azetidine-Pd catalytic combinations. Synthesis and evaluation of the ligand ring size impact on Suzuki reaction issues.
Authors: Hamza Boufroura 1, Benjamin Large 1, Talia Bsaibess 1, Serge Perato 1, Anne gaucher 1, and Damien Prim 1,*
Affiliation: 1 Université de Versailles Saint-Quentin-en-Yvelines, Institut Lavoisier de Versailles, UMR CNRS 8180, 45, Avenue des Etats-Unis, 78035 Versailles
*Correspondence: damien.prim@uvsq.fr; Tel.: +33-013-925-4455
Abstract: The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki coupling reaction are described in this communication. The synthesis of three- and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four news catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine- and azetidine-based catalytic systems allowed Suzuki reactions from aryl bromides and chlorides with catalytic loadings until 0.1% at temperatures ranging from 100° to rt. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or a imidate pendant arm impacted the the Suzuki reaction issue.
Keywords: aziridine; azetidine; vicinal diamine; ligand; Suzuki

Title: Aqueous Suzuki Coupling Reactions of Basic Nitrogen-Containing Aryl Chlorides in the Absence of Added Base: Observation of High Yields under Acidic Conditions
Authors: Zhao Li, Carol Gelbaum, Jason S. Fisk§, Bruce Holden§, Arvind Jaganathan§, Gregory T. Whiteker£, Pamela Pollet, and Charles L. Liotta*†‡
Affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, USA
The Dow Chemical Company, Midland, Michigan 48674, USA
£Dow AgroSciences, Indianapolis, Indiana 46268, USA
Keywords: aqueous Suzuki reactions, aryl chlorides, P-ligands, base-free, acidic conditions, oxo palladium mechanism
Abstract: A series of aqueous heterogeneous Suzuki coupling reactions of aryl chlorides containing basic nitrogen centers with arylboronic acids in the absence of added base using commercial P-ligands is presented. High yields of products were obtained employing aryl chlorides containing aliphatic amine substituents and good to high yields were obtained employing a variety of substituted chloropyridines. In the former series, the pH of the aqueous phase changed from basic to acidic during the course of reaction while in the latter series, the entire course of coupling reactions took place under acidic conditions. A mechanistic interpretation for these observations is presented.

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