C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• Pd-catalyzed Suzuki–Miyaura reaction. The C–H bond activation process was believed to be initiated by the oxidation effect of the Cu(II) catalyst to give intermediate 54 which was further oxidized to provide cation intermediate 55. The deprotection of 55 gave finally the halogenated products 52

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• C–H borylation of several 1-substituted-3-(pentafluorosulfanyl)benzenes and applied the products of borylation to the Pd-catalyzed Suzuki–Miyaura reaction with aryl bromides or iodides. However, the reaction is limited to borylations in position five of 1-substituted-3-(pentafluorosulfanyl)benzenes

• [72]. Straightforward access to SF5-phenylboronic acids or boronates would be highly desirable since it would allow easy installation of the SF5-phenyl group by the subsequent Suzuki–Miyaura reaction. Nitro-(pentafluorosulfanyl)benzenes are the primary industrial SF5-aromatics, therefore the easiest

• electron-donor or acceptor groups while ortho-substituted substrates are less reactive. A mechanism involving aryl radicals is suggested. The Suzuki–Miyaura reaction of SF5-phenylboronates with aryl iodides provided the cross-coupling biaryl products. In analogy to the borylation reaction, iodination of

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation

• Vadim V. Bardin,
• Anton Yu. Shabalin and
• Nicolay Yu. Adonin

Beilstein J. Org. Chem. 2015, 11, 608–616, doi:10.3762/bjoc.11.68

• correlation between the reactivity of K[4-RC6F4BF3] and substituent electron parameters, σI and σR°, of the aryl group 4-RC6F4 was found. Keywords: potassium polyfluoroaryltrifluoroborate; silver(I) acceleration; Suzuki–Miyaura reaction; Introduction The palladium-catalyzed reaction of organoboron compounds

• with C-electrophiles (Suzuki–Miyaura reaction) is one of the most intensively studied processes of the carbon–carbon bond formation. Organoboronic acids, their esters and organotrifluoroborates are partners in these reactions and the choice of the desired reagent depends on the specific requirements in

• salts 1b–p (1:1) with 11 (the results are presented in Table 3 and outlined in the Discussion section). The cross-coupling of 1a with 11 in the presence of different silver(I) compounds. General concept of Pd-catalyzed Suzuki–Miyaura reaction. Assumed silver(I)-assisted transmetallation of weakly

Clean and fast cross-coupling of aryl halides in one-pot

• Valerica Pandarus,
• Geneviève Gingras,
• François Béland,
• Rosaria Ciriminna and
• Mario Pagliaro

Beilstein J. Org. Chem. 2014, 10, 897–901, doi:10.3762/bjoc.10.87

• Unsymmetrically coupled biaryls are synthesized in high yield starting from different aryl bromides and bis(pinacolato)diboron by carrying out the Miyaura borylation reaction followed by the Suzuki–Miyaura reaction in the same reaction pot over 1–2 mol % SiliaCat DPP-Pd. The SiliaCat DPP-Pd catalyst is air-stable

• involves a boron-containing nucleophile (a variety of aryl and heteroaryl boronic acids, esters, Ar-BBN, trifluoroborate and other boron species) and vinyl- or aryl halides as the electrophilic species. The use of the Suzuki–Miyaura reaction became routine both in industry and in research laboratories

• Suzuki–Miyaura reaction when reactive functional groups are present in the electrophilic aryl halides [3][4]. Several homogeneous palladium catalysts of enhanced versatility for the cross-coupling of pinacolborane with aryl halides have since been introduced, for example by Buchwald and co-workers [5][6

Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: efficient synthesis of 1,1-diaryl-2,2-difluoroethenes

• Ju Hee Kim,
• Su Jeong Choi and
• In Howa Jeong

Beilstein J. Org. Chem. 2013, 9, 2470–2475, doi:10.3762/bjoc.9.286

• . Since the use of a proper base in the Suzuki–Miyaura reaction is an important factor to increase the yield of coupled product, we screened bases to get the optimized reaction conditions. When 2 was reacted with 1 equiv of phenylboronic acid in the presence of 5 mol % of Pd(OAc)2 and Cs2CO3 (2 equiv) in

ML212: A small-molecule probe for investigating fluconazole resistance mechanisms in Candida albicans

• Willmen Youngsaye,
• Cathy L. Hartland,
• Barbara J. Morgan,
• Amal Ting,
• Partha P. Nag,
• Benjamin Vincent,
• Carrie A. Mosher,
• Joshua A. Bittker,
• Sivaraman Dandapani,
• Michelle Palmer,
• Luke Whitesell,
• Susan Lindquist,
• Stuart L. Schreiber and
• Benito Munoz

Beilstein J. Org. Chem. 2013, 9, 1501–1507, doi:10.3762/bjoc.9.171

• Two different routes were adopted to access the various functionalized indazoles required to evaluate the SAR associated with hit compound 1 (Scheme 1). The robust Suzuki–Miyaura reaction was selected for the preparation of analogues bearing substituents around the central indazole core. This approach

Camera-enabled techniques for organic synthesis

• Steven V. Ley,
• Richard J. Ingham,
• Matthew O’Brien and
• Duncan L. Browne

Beilstein J. Org. Chem. 2013, 9, 1051–1072, doi:10.3762/bjoc.9.118

• reported the application of the synthetically powerful Suzuki–Miyaura reaction within aqueous microdroplets buffered by catalytically active fluorous interfaces [45]. Images of the flow channels captured by a high-speed camera provided preliminary kinetic data by allowing the precipitation of the solid

• setup that might not otherwise be available. Suzuki–Miyaura reaction performed within a microfluidic system. The product is observed by high-speed microscope photography, which shows a precipitate forming within the microdroplets. Friedel–Crafts reactions performed by using solid-acid catalysis at high

Scaling up of continuous-flow, microwave-assisted, organic reactions by varying the size of Pd-functionalized catalytic monoliths

• Ping He,
• Stephen J. Haswell,
• Paul D. I. Fletcher,
• Stephen M. Kelly and
• Andrew Mansfield

Beilstein J. Org. Chem. 2011, 7, 1150–1157, doi:10.3762/bjoc.7.133

• , respectively. Under optimal reaction conditions the quantity of product could be increased from 31 mg per hour to 340 mg per hour simply by changing the volumetric capacity of the monolith. Keywords: continuous flow; microwave heating; monolith; scaling-up; Suzuki–Miyaura reaction; Introduction Interest in

• the Pd-monolith catalyst The Suzuki–Miyaura reaction is a widely used method in organic synthesis for the selective formation of aryl–aryl carbon–carbon bonds in the synthesis of high-value fine chemicals and intermediates in the pharmaceutical industry. This reaction requires a metal catalyst, such

• as palladium, in both homogeneous and heterogeneous reactions. In this study, the Suzuki–Miyaura reaction of bromobenzene with phenylboronic acid (Scheme 1) was initially used as a model heterogeneously catalyzed reaction for the evaluation of Pd-monolith activity under continuous flow conditions

Synthesis of chiral mono(N-heterocyclic carbene) palladium and gold complexes with a 1,1'-biphenyl scaffold and their applications in catalysis

• Lian-jun Liu,
• Feijun Wang,
• Wenfeng Wang,
• Mei-xin Zhao and
• Min Shi

Beilstein J. Org. Chem. 2011, 7, 555–564, doi:10.3762/bjoc.7.64

• showed good catalytic activities in the asymmetric intramolecular hydroamination reaction to give the corresponding product in moderate ee. Keywords: chiral mono(N-heterocyclic carbene) complex; Heck–Mizoroki reaction; hydroamination; Suzuki–Miyaura reaction; Introduction N-heterocyclic carbene (NHC

• (II) complex. Synthesis of mono(NHC)–Au(I) complex. Synthesis of mono(NHC)–Au(I) complex (S)-6b. Synthesis of mono(NHC)–Au(I) complex (S)-6c. The application of catalysts (S)-6b and 6c in the intramolecular hydroamination reaction. Suzuki–Miyaura reaction catalyzed by NHC–Pd(II) complex 7a. Heck

Air-stable, recyclable, and time-efficient diphenylphosphinite cellulose-supported palladium nanoparticles as a catalyst for Suzuki–Miyaura reactions

• Qingwei Du and
• Yiqun Li

Beilstein J. Org. Chem. 2011, 7, 378–385, doi:10.3762/bjoc.7.48

• Qingwei Du Yiqun Li Department of Chemistry, Jinan University, 510632 Guangzhou, China 10.3762/bjoc.7.48 Abstract A diphenylphosphinite cellulose palladium complex (Cell–OPPh2–Pd0) was found to be a highly efficient heterogeneous catalyst for the Suzuki–Miyaura reaction. The products were

• catalyst; Suzuki–Miyaura reaction; Introduction The formation of Csp2–Csp2 bonds has long remained a difficult task until the development of the Suzuki–Miyaura palladium-catalyzed reaction [1][2][3]. The palladium-catalyzed Suzuki cross-coupling reaction of aryl halides with arylboronic acids is one of

• proved to be the best and was thus chosen as the base in the Suzuki–Miyaura reaction. From Table 2, we found that using 95% ethanol as the solvent gave the highest yield, i.e., 93% (Table 2, entries 1–8). The results in Table 3 showed that the loading of catalyst has an effect on the yield. When 0.15

Suzuki–Miyaura cross-coupling reaction of 1-aryltriazenes with arylboronic acids catalyzed by a recyclable polymer-supported N-heterocyclic carbene–palladium complex catalyst

• Guangming Nan,
• Fang Ren and
• Meiming Luo

Beilstein J. Org. Chem. 2010, 6, No. 70, doi:10.3762/bjoc.6.70

• ; recyclable catalyst; Suzuki–Miyaura reaction; Introduction The unsymmetrical biaryls feature in a diverse range of organic compounds, such as natural products, advanced materials, liquid crystals, ligands and molecules of medicinal interest [1][2][3][4]. The palladium-catalyzed Suzuki–Miyaura cross-coupling

Solvent-free and time-efficient Suzuki–Miyaura reaction in a ball mill: the solid reagent system KF–Al₂O₃ under inspection

• Franziska Bernhardt,
• Ronald Trotzki,
• Tony Szuppa,
• Achim Stolle and
• Bernd Ondruschka

Beilstein J. Org. Chem. 2010, 6, No. 7, doi:10.3762/bjoc.6.7

• KF-loaded aluminas is available in the literature, there is almost no data concerning the influence of parameters such as alumina modification or KF-loading on experimental results. Hence, the Pd-catalyzed, solvent-free Suzuki–Miyaura reaction was chosen as model reaction to investigate the effect of

• comminuting the reactants for just 10 min [40][41] without the presence of any additional stabilizing or activating ligands. Compared to the original published procedure for the Suzuki–Miyaura reaction [36] or the protocols featured by Mack and Frejd and their coworkers for Sonogashira [54] and Heck–Jeffery

• neutral to basic aluminas has been recently shown in three-component reactions affording thiochromeno[2,3-b]pyridine derivatives [24]. The results were in clear contrast to that of the microwave-assisted Pd(PPh3)4-catalyzed solid-state Suzuki–Miyaura reaction protocol presented by Saha et al., revealing

Polyionic polymers – heterogeneous media for metal nanoparticles as catalyst in Suzuki–Miyaura and Heck–Mizoroki reactions under flow conditions

• Klaas Mennecke and
• Andreas Kirschning

Beilstein J. Org. Chem. 2009, 5, No. 21, doi:10.3762/bjoc.5.21

• ; microreactor; monolith; palladium; Suzuki–Miyaura reaction; Introduction Functionalized solid supports like polymers loaded with homogeneous catalysts are well established in organic synthesis [1][2][3][4]. Simple purification of the products and easy recyclability of the catalysts are major advantages of

• nanoparticles (7–10 nm in size and a palladium content of 0.03 weight% Pd on polyionic polymer). Suzuki–Miyaura cross coupling reactions In our earlier work we showed that these materials are well suited for transfer hydrogenations under flow conditions [23][24]. Recently, the Suzuki–Miyaura reaction and other

• palladium catalyzed reactions have emerged as industrially very desirable processes and miniflow fixed bed reactors loaded with Pd(0) nanoparticles should be well suited to perform these C-C coupling reactions [34]. A particular challenge for utilizing the Suzuki–Miyaura reaction in flow devices is the

Oxidative cyclization of alkenols with Oxone using a miniflow reactor

• Yoichi M. A. Yamada,
• Kaoru Torii and
• Yasuhiro Uozumi

Beilstein J. Org. Chem. 2009, 5, No. 18, doi:10.3762/bjoc.5.18

• laminar flow interface [16], resulting in the instantaneous production of biaryls (quantitative yield within 4 s of residence time) via a palladium-catalyzed Suzuki-Miyaura reaction under microflow conditions. An additional advantage of micro- and minireactors is the small heat capacity of the micro- and

Convenient methods for preparing π-conjugated linkers as building blocks for modular chemistry

• Jiří Kulhánek,
• Filip Bureš and
• Miroslav Ludwig

Beilstein J. Org. Chem. 2009, 5, No. 11, doi:10.3762/bjoc.5.11

• use as building blocks in Suzuki–Miyaura or Sonogashira coupling reactions. Keywords: boronic acid; donor/acceptor; linker; Sonogashira reaction; property tuning; push-pull; Suzuki–Miyaura reaction; Introduction Development of new organic compounds with improved and advanced properties is one of the