An effective Pd nanocatalyst in aqueous media: stilbene synthesis by Mizoroki–Heck coupling reaction under microwave irradiation

• Carolina S. García,
• Paula M. Uberman and
• Sandra E. Martín

Beilstein J. Org. Chem. 2017, 13, 1717–1727, doi:10.3762/bjoc.13.166

• with a magnetic stirring bar, aryl halide 1a–h (0.25 mmol), K2CO3 (0.5 mmol), olefin 2a–d (0.3 mmol), ethanol (0.5 mL) and water (to obtain a total volume of 2 mL taking into account the volume of Pd NPs solution) were added. Finally, the required volume of the Pd NPs dispersion was added. Then, the

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• , mild reaction conditions, and easy access to starting materials. 1.1 Aryl halide as substrate Compared with other traditional starting materials, such as phenylsulfonic acid, aryl ketone and phenylboronic acid [17][18][19][20], aryl halides can be considered as simple and economical starting materials

• : In 2006, Buchwald and co-workers described the first synthesis of phenols from aryl halides through a palladium-catalyzed reaction [21]. The C–O coupling reaction of an aryl halide and potassium hydroxide took place when using Pd2dba3 as catalyst, biphenylphosphine (L1 or the bulkier L2) as ligand

Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis

• Flavio Fanelli,
• Giovanna Parisi,
• Leonardo Degennaro and
• Renzo Luisi

Beilstein J. Org. Chem. 2017, 13, 520–542, doi:10.3762/bjoc.13.51

• different aryl halide (Ar2X). Without requiring the protection of sensitive functionalities, running the flow system using a residence time (tR) of about 4.7 min at a temperature above 100 °C, high yields of coupling products were obtained. Noteworthy, the Suzuki–Miyaura coupling did not require the use of

Efficient access to β-vinylporphyrin derivatives via palladium cross coupling of β-bromoporphyrins with N-tosylhydrazones

• Vinicius R. Campos,
• Ana T. P. C. Gomes,
• Anna C. Cunha,
• Maria da Graça P. M. S. Neves,
• Vitor F. Ferreira and
• José A. S. Cavaleiro

Beilstein J. Org. Chem. 2017, 13, 195–202, doi:10.3762/bjoc.13.22

• biological properties or might become important templates for further functionalization procedures (Scheme 2). Results and Discussion For this work 2-bromo-5,10,15,20-tetraphenylporphyrinatozinc(II) (1) was used as the aryl halide and also the easily accessible N-tosylhydrazones 2a–c (Scheme 3). Both

Chromium(II)-catalyzed enantioselective arylation of ketones

• Gang Wang,
• Shutao Sun,
• Ying Mao,
• Zhiyu Xie and
• Lei Liu

Beilstein J. Org. Chem. 2016, 12, 2771–2775, doi:10.3762/bjoc.12.275

• -substituted ketone (1i) were also suitable substrate, giving product 2i in 78% ee. The scope of the aryl halide component was next explored (1j–l). Aryl halides bearing different substituent patterns were tolerated giving the tetrahydronaphthalen-1-ols with good ee values. When 4-(2-iodophenyl)butan-2-one (1m

Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I)

• Sem Raj Tamang and
• James D. Hoefelmeyer

Beilstein J. Org. Chem. 2016, 12, 2757–2762, doi:10.3762/bjoc.12.272

• , MA, USA). Catalysis experiments. A 50 mL roundbottom flask was charged with 0.5 mmol of aryl halide, benzene (4 mL) and 1.5 mmol of KO(t-Bu). The flask was fitted with a reflux condenser left open to air. Then, a solution of catalyst dissolved in 420 μL DMF was added to the reaction. The reaction was

Flow carbonylation of sterically hindered ortho-substituted iodoarenes

• Carl J. Mallia,
• Gary C. Walter and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2016, 12, 1503–1511, doi:10.3762/bjoc.12.147

• aryl halide, an associative mechanism for the complexation of carbon monoxide on the d8 square planar intermediate would occur prior to the key migratory insertion step. In the complex, the aryl group would be oriented perpendicularly to the plane to minimise steric interactions thus placing the ortho

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• chelating ligands and thus compete with the chiral ligand for binding with the copper salts. Therefore the authors used a mono-aryl halide-substituted malonamide in the presence of a chiral CuI/1,2-diamine catalyst system and obtained the desired products in good yields and moderate enantioselectivities [48

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η⁵-Cp)Pd(IPr)Cl with (η³-cinnamyl)Pd(IPr)(Cl) and (η³-1-t-Bu-indenyl)Pd(IPr)(Cl)

• Patrick R. Melvin,
• Nilay Hazari,
• Hannah M. C. Lant,
• Ian L. Peczak and
• Hemali P. Shah

Beilstein J. Org. Chem. 2015, 11, 2476–2486, doi:10.3762/bjoc.11.269

• the olefin ligand from C generates the active monoligated Pd(0) species, which in catalysis undergoes oxidative addition with the aryl halide, but in the case of our activation experiments is trapped by dvds. The considerably faster rate of activation for Cp compared to Cin, suggests that Cp should be

Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

• Svetlana P. Panchenko,
• Alexei D. Averin,
• Maksim V. Anokhin,
• Olga A. Maloshitskaya and
• Irina P. Beletskaya

Beilstein J. Org. Chem. 2015, 11, 2297–2305, doi:10.3762/bjoc.11.250

• , it has been found that to obtain a good result, the reaction conditions (ligand, solvent, temperature) should be adjusted for a certain aryl halide/polyamine pair. In the present study we decided to undertake a thorough investigation of the Cu(I)-catalyzed N,N’-diarylation of natural diamines and

Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

• Mohamed Yacine Ameur Messaoud,
• Ghenia Bentabed-Ababsa,
• Madani Hedidi,
• Aïcha Derdour,
• Floris Chevallier,
• Yury S. Halauko,
• Oleg A. Ivashkevich,
• Vadim E. Matulis,
• Laurent Picot,
• Valérie Thiéry,
• Thierry Roisnel,
• Vincent Dorcet and
• Florence Mongin

Beilstein J. Org. Chem. 2015, 11, 1475–1485, doi:10.3762/bjoc.11.160

• synthesis of derivatives 1f and 2f, we rather employed 1.2 equiv of the aryl halide, 0.05 equiv of copper(I) iodide, 0.10 equiv of N,N’-dimethylethylenediamine (DMEDA), 2 equiv of tripotassium phosphate in dimethylformamide as the solvent at 120 °C [45]. Under these conditions, the N-(4-(trifluoromethyl

• the synthesis of the N-arylated pyrroles and indoles 1a,b,d,e and 2a–e [44]. To azole (6.0 mmol) and aryl halide (4.0 mmol) in acetonitrile (20 mL) were successively added Cu (50 mg, 0.80 mmol), Cs2CO3 (2.6 g, 8.0 mmol) and, in the case of aryl bromides, KI (99 mg, 6.0 mmol). The mixture was stirred

• expected compounds. Procedure 2 for the synthesis of the N-arylated pyrroles and indoles 1f and 2f [45]. To azole (10 mmol) and aryl halide (12 mmol) in DMF (5 mL) were successively added CuI (95 mg, 0.50 mmol), K3PO4 (4.2 g, 20 mmol) and DMEDA (0.11 mL, 1.0 mmol). The mixture was stirred under argon at

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• sterically hindered pyrrole-H. The highest yielding reactions under sealed tube conditions gave comparable yields to the lowest yielding reactions under microwave conditions. In general, the microwave conditions give high yields and can tolerate a range of functional groups on the aryl halide. We believe

A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

• Claudia A. Contreras-Celedón,
• Darío Mendoza-Rayo,
• José A. Rincón-Medina and
• Luis Chacón-García

Beilstein J. Org. Chem. 2014, 10, 2821–2826, doi:10.3762/bjoc.10.299

• organic reactions. Synthesis of 4-aminoantipyrine-Pd(II) complex. Reaction of different aryl halides with substituted arylboronic acids. Reaction conditions: phenylboronic acid (0.40 mmol), aryl halide (0.27 mmol), 4-AAP–Pd(II) (0.3 mol %), 2 M K2CO3 (0.67 mmol), ethanol (2 mL), heating under reflux for 4

Multicomponent reactions in nucleoside chemistry

• Mariola Koszytkowska-Stawińska and
• Włodzimierz Buchowicz

Beilstein J. Org. Chem. 2014, 10, 1706–1732, doi:10.3762/bjoc.10.179

• nucleosides 93 were also prepared by this method. 7. The carbopalladation of dienes A reaction of an aryl halide, an unsaturated alkene (diene, allene), and an amine catalyzed by Pd(0) species, referred to as carbopalladation of dienes, results in the three-component assembly of an unsaturated amine (Scheme

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

• Jingran Tao,
• Li-Mei Jin and
• X. Peter Zhang

Beilstein J. Org. Chem. 2014, 10, 1282–1289, doi:10.3762/bjoc.10.129

• -subtituted styrene 1e (Table 2, entry 5), the catalytic reaction of the sterically demanding o-Br-substituted olefin 1k gave the desired aziridine in almost quantitative yield as well as high enantioselectivity (Table 2, entry 11). It is worthy to mention that the aryl halide units of these chiral aziridines

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• approach towards the widely used arylphosphines that are inaccessible by hydrophosphination. Recent advances in this area concern the synthesis of P-stereogenic phosphines through a dynamic kinetic resolution of racemic secondary phosphines in a metal-catalyzed P–H/aryl halide coupling. C(sp2)–P bond

• tertiary phosphines 118 via the cross-coupling of aryl triflates and halides 117 with chlorodiphenylphosphine (22a) instead of diphenylphosphine (Table 12) [53]. The reaction was catalyzed by NiCl2(dppe) in the presence of zinc. A hydrodehalogenation side reaction resulted in lower yields of aryl halide

A new manganese-mediated, cobalt-catalyzed three-component synthesis of (diarylmethyl)sulfonamides

• Antoine Pignon,
• Erwan Le Gall and
• Thierry Martens

Beilstein J. Org. Chem. 2014, 10, 425–431, doi:10.3762/bjoc.10.39

• in situ activation (Barbier conditions) of the aryl halide by cobalt salts in the presence of a reducing metal. Initial experiments employed zinc as the reducing agent and were carried out under standard conditions. However, only trace amounts of the coupling product were detected in the reaction

• of the reaction. Aryl halide is generally prone to dimerization under such reductive conditions. Thus, we assume that if the imine is formed slowly or is less reactive, the more rapid consumption of the halide results in the lack of a nucleophilic partner in the reaction medium. In this case, the

• was previously established that zinc is able to reduce cobalt(II) in the presence of an aryl halide to promote the formation of a transient arylcobalt(II) species, which undergoes a fast transmetallation with zinc to furnish an organozinc species [39]. It can thus be assumed that a reductive metal

Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

• Andrea Caporale,
• Stefano Tartaggia,
• Andrea Castellin and
• Ottorino De Lucchi

Beilstein J. Org. Chem. 2014, 10, 384–393, doi:10.3762/bjoc.10.36

• presence of a Cu/Pd bimetallic catalyst, followed by the basic cleavage of the protecting group [42][43][44][45][46]. Terminal alkynes are often used as starting materials for the synthesis of disubstituted acetylenes through a second coupling process with another aryl halide. Decarboxylative couplings

Boron-substituted 1,3-dienes and heterodienes as key elements in multicomponent processes

• Ludovic Eberlin,
• Fabien Tripoteau,
• François Carreaux,
• Andrew Whiting and
• Bertrand Carboni

Beilstein J. Org. Chem. 2014, 10, 237–250, doi:10.3762/bjoc.10.19

• -coupled using palladium catalysis. A one-pot sequence was also developed, first heating the boron diene with the dienophile, then adding an aryl halide, Pd(OAc)2 (5 mol %), K2CO3 (3 equiv) and finally refluxing the mixture in EtOH or MeOH for 5 h (Scheme 13). Reactions with various aryl halides

Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

• Phei Li Lau,
• Ray W. K. Allen and
• Peter Styring

Beilstein J. Org. Chem. 2013, 9, 2886–2897, doi:10.3762/bjoc.9.325

• system over homogeneously catalysed reactions using complexes with elaborate ligand design, it would also make purification simpler. Results and Discussion Two reactions were studied using continuous flow chemistry as shown in Scheme 1. In both cases 4-iodoanisole was used as the aryl halide. The alkene

• palladium metal-catalysed Heck reaction between an aryl halide and an alkene under continuous flow conditions in a plug flow reactor (PFR). The efficiency of the reaction depends on the nature of the alkene used, the temperature and pressure of the reaction and the flow rate of the reagents over the fixed

An easy direct arylation of 5-pyrazolones

• Hao Gong,
• Yiwen Yang,
• Zechao Wang and
• Chunxiang Kuang

Beilstein J. Org. Chem. 2013, 9, 2033–2039, doi:10.3762/bjoc.9.240

• Education, Shanghai 200092, China 10.3762/bjoc.9.240 Abstract A mild, efficient and catalytic ligand-free method for the direct arylation of 5-pyrazolones by Pd-catalyzed C–H bond activation is reported. The process smoothly proceeds and yields are moderate to excellent. Keywords: arylation; aryl halide

N-Heterocyclic carbene–palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides

• Ismail Özdemir,
• Nevin Gürbüz,
• Nazan Kaloğlu,
• Öznur Doğan,
• Murat Kaloğlu,
• Christian Bruneau and
• Henri Doucet

Beilstein J. Org. Chem. 2013, 9, 303–312, doi:10.3762/bjoc.9.35

• limitations for these reactions in terms of aryl halide or heteroaromatic tolerance. Up to now, very few examples of palladium-catalyzed direct arylations of pyrroles by using aryl chlorides have been reported, [26][27]. Daugulis and co-workers recently described the arylation of pyrrole derivatives with a

Organocatalytic C–H activation reactions

• Subhas Chandra Pan

Beilstein J. Org. Chem. 2012, 8, 1374–1384, doi:10.3762/bjoc.8.159

• LUMO and thus accepts an electron to generate a radical anion, and then passes the electron to aryl halide [35]. A general mechanism for the organocatalytic cross-coupling reactions was proposed by Studer and Curran [36], which suggests a “base-promoted homolytic aromatic substitution” mechanism. In

Synthesis of oleophilic electron-rich phenylhydrazines

• Aleksandra Jankowiak and
• Piotr Kaszyński

Beilstein J. Org. Chem. 2012, 8, 275–282, doi:10.3762/bjoc.8.29

• deprotection of hydrazides II have been developed (Figure 1). Hydrazides II are efficiently obtained by the addition of organometallic reagents III, prepared from aryl halide IV, to azodicarboxylate diesters (AD) [16][17]. Alternatively, II can be obtained in the Pd(0)- or Cu2+-catalyzed reaction of

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• , oxidative addition of the aryl halide to the Pd(0) catalyst generates an organopalladium reagent, which activates the alkyne moiety towards nucleophilic attack of the amino group. A reductive elimination generates the indole derivatives 59. In this one-pot three-component reaction, the same palladium