Synthesis and fluorosolvatochromism of 3-arylnaphtho[1,2-b]quinolizinium derivatives

• Phil M. Pithan,
• David Decker,
• Manlio Sutero Sardo,
• Giampietro Viola and
• Heiko Ihmels

Beilstein J. Org. Chem. 2016, 12, 854–862, doi:10.3762/bjoc.12.84

• Pharmacological Sciences, via Marzolo 5, 35131 Padova, Italy University of Padova, Department of Woman’s and Child’s health, 35128 Padova, Italy 10.3762/bjoc.12.84 Abstract Cationic biaryl derivatives were synthesized by Suzuki–Miyaura coupling of 3-bromonaphtho[1,2-b]quinolizinium bromide with arylboronic acids

• -arylnaphtho[1,2-b]quinolizinium derivatives and demonstrate that some of these compounds have fluorosolvatochromic properties. Results Synthesis The 3-arylnaphtho[1,2-b]quinolizinium derivatives 6a–e were prepared by Suzuki–Miyaura coupling reactions with the 3-bromonaphtho[1,2-b]quinolizinium bromide (4

• -benzylpyridinium derivative 3 and the subsequent cyclodehydration [27] in refluxing HBr (w = 48%) gave the bromonaphtho[1,2-b]quinolizinium 4 in 57% overall yield (Scheme 1). The Suzuki–Miyaura coupling reactions of 3-bromonaphthoquinolizinium derivative 4 with the arylboronic acids 5a–e were performed under

A convenient route to symmetrically and unsymmetrically substituted 3,5-diaryl-2,4,6-trimethylpyridines via Suzuki–Miyaura cross-coupling reaction

• Dariusz Błachut,
• Joanna Szawkało and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2016, 12, 835–845, doi:10.3762/bjoc.12.82

• substituted 3,5-diaryl-2,4,6-trimethylpyridines were prepared and characterized using the Suzuki–Miyaura coupling reaction with accordingly selected bromo-derivatives and arylboronic acids. The reaction conditions were carefully optimized allowing high yield of isolated products and also the construction of

• convenient synthesis of symmetrically and unsymmetrically substituted 3,5-diaryl-2,4,6-trimethylpyridines via Suzuki–Miyaura cross-coupling reaction. Several diarylpyridines with mixed aryl rings were produced by sequential two-step Suzuki cross-coupling reaction with separation of intermediary 3-aryl-5

Syntheses of dibenzo[d,d']benzo[2,1-b:3,4-b']difuran derivatives and their application to organic field-effect transistors

• Minh Anh Truong and
• Koji Nakano

Beilstein J. Org. Chem. 2016, 12, 805–812, doi:10.3762/bjoc.12.79

• -isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (iPrO-Bpin) gave boronate ester 7 in 57% yield. Then, terphenyl 9 was synthesized via palladium-catalyzed Suzuki–Miyaura cross coupling of boronate ester 7 with 2,3-difluoro-1,4-diiodobenzene (96% yield) and subsequent demethylation (95% yield). Finally, the

Spiro-fused carbohydrate oxazoline ligands: Synthesis and application as enantio-discrimination agents in asymmetric allylic alkylation

• Jochen Kraft,
• Martin Golkowski and
• Thomas Ziegler

Beilstein J. Org. Chem. 2016, 12, 166–171, doi:10.3762/bjoc.12.18

• benzylation, fully characterized and subjected to palladium catalyzed Suzuki–Miyaura coupling with 2-pyridineboronic acid N-phenyldiethanolamine ester to give the corresponding 2-pyridyl spiro-oxazoline (PyOx) ligands. The spiro-oxazoline ligands showed high asymmetric induction (up to 93% ee) when applied as

• these compounds slowly start to decompose after 2 weeks at −28 °C under an atmosphere of nitrogen. Next, benzylsulfanyloxazolines 7 and 8 were subjected to copper-assisted palladium-catalyzed Suzuki–Miyaura-type cross coupling with commercially available 2-pyridineboronic acid N-phenyldiethanolamine

• cross coupling of the latter under modified Suzuki–Miyaura conditions. The prepared ligands were shown to be active precatalysts for the asymmetric allylic alkylation of 1,3-diphenylallyl acetate with dimethyl malonate. The D-fructo-configurated ligands provided the (R)-enantiomer with up to 93% ee

Hydroquinone–pyrrole dyads with varied linkers

• Hao Huang,
• Christoffer Karlsson,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 89–96, doi:10.3762/bjoc.12.10

• . achieved a total yield of 70% [11], however, their procedure relies on a Wolff–Kishner reduction of the corresponding acylpyrrole with hydrazine hydrate, making it impractical in countries where the use of hydrazine has been restricted by law [12]. As an alternative, the Suzuki–Miyaura reaction can be

• considered satisfactory because of the ready availability of starting materials and the modest reaction time of 4 hours. Since the starting materials in the Suzuki–Miyaura cross-coupling tolerate a wide variety of functional groups, facile and versatile combination of different dihydroxybenzyl halide

• utilized for C–C cross coupling of benzyl halides with heteroarylboronic acids. However, in contrast to its use for the synthesis of thiophene and furane derivatives, it has rarely been employed for the coupling of pyrrolylboronic acids with benzyl halides [13][14][15][16][17]. We applied the Suzuki

N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions

• Senem Akkoç,
• Yetkin Gök,
• İlhan Özer İlhan and
• Veysel Kayser

Beilstein J. Org. Chem. 2016, 12, 81–88, doi:10.3762/bjoc.12.9

• -alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of 1H and 13C{1H} NMR, UV–vis (for 5–8), ESI-FTICR-MS (for 2, 4, 6–8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki–Miyaura cross-coupling (for 1–8) and

• with 4-chlorotoluene. Keywords: arylation; benzimidazolium salts; catalysis; N-heterocyclic carbene; PEPPSI complex; Suzuki–Miyaura cross-coupling reaction; Introduction The use of N-heterocyclic carbenes (NHCs) as ligands was started by Wanzlick [1] and Öfele [2] almost fifty years ago. There have

• complexes have been used in different coupling reactions such as Mizoroki–Heck cross-coupling [22][23], Suzuki–Miyaura cross-coupling [24][25], Sonogashira [26] and arylation reactions [27]. There are suitable precatalyst scaffolds, which were developed by Nolan [28], Organ [21] and Buchwald [29]. To find

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• (PdNPs) affording highly active catalysts for Suzuki–Miyaura coupling reactions. Cobalt-containing polymers The incorporation of other late transition metals such as cobalt into polymers soon emerged as an efficient and rapid method for the production of nanostructured materials of scientific and

Synthesis of Xenia diterpenoids and related metabolites isolated from marine organisms

• Tatjana Huber,
• Lara Weisheit and
• Thomas Magauer

Beilstein J. Org. Chem. 2015, 11, 2521–2539, doi:10.3762/bjoc.11.273

• iodide 97. The following palladium-catalyzed B-alkyl Suzuki–Miyaura cross coupling between the borane derived from alkene 98 and vinyl iodide 97 furnished a Z-configured alkene. Deprotection of the trimethylsilyl ether then afforded alcohol 99. A rhodium(II)-catalyzed O–H insertion reaction of the

• -membered carbocycle was realized via a B-alkyl Suzuki–Miyaura cross-coupling reaction. Optimization studies of this key ring closure with different protecting groups on the lactol functionality revealed methyl acetal 135 as the most efficient substrate for this transformation. The challenging key step was

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

• precatalysts for the Suzuki–Miyaura reaction. Even though allyl and indenyl ligands are similar to cyclopentadienyl (Cp) ligands, there have been no detailed comparative studies exploring the activity of precatalysts of the type (η5-Cp)Pd(L)(Cl) for Suzuki–Miyaura reactions. Here, we compare the catalytic

• . As part of this work the Cp supported Pd(I) dimer (μ-Cp)(μ-Cl)Pd2(IPr)2 (CpDim) was synthesized and crystallographically characterized. It does not readily disproportionate to form monoligated Pd(0) and consequently CpDim is a poor catalyst for the Suzuki–Miyaura reaction. Keywords: cross-coupling

• ; homogeneous catalysis; NHC ligands; palladium; Suzuki–Miyaura reaction; Introduction The Suzuki–Miyaura reaction is a powerful synthetic method for forming C–C bonds between aryl halides or pseudo halides and organoborane containing species [1][2][3][4][5]. The most active catalysts are generally based on Pd

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

• Johnathon Yau,
• Kaarel E. Hunt,
• Laura McDougall,
• Alan R. Kennedy and
• David J. Nelson

Beilstein J. Org. Chem. 2015, 11, 2171–2178, doi:10.3762/bjoc.11.235

• . The new species were fully characterised using methods including NMR spectroscopy and X-ray crystallography. When tested in model Suzuki–Miyaura cross-coupling reactions, these complexes were found to be active for the cross-coupling of aryl bromides and aryl chlorides. Keywords: catalysis; cross

• NHC·HCl salt, rendering these species highly accessible (Scheme 1b) [10]. After the initial work by Cowley and Jones, various other researchers have disclosed complexes of this form and tested them in cross-coupling reactions such as Buchwald–Hartwig amination [11], Suzuki–Miyaura cross-coupling [12], and

• )] complexes in Suzuki–Miyaura cross-coupling reactions of 4’-bromoacetophenone and 4’-chloroacetophenone with phenylboronic acid (Scheme 4) [12]. It was therefore decided to study these reactions as part of our preliminary evaluation of these new complexes as potential pre-catalysts for cross-coupling

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

The simple production of nonsymmetric quaterpyridines through Kröhnke pyridine synthesis

• Isabelle Sasaki,
• Jean-Claude Daran and
• Gérard Commenges

Beilstein J. Org. Chem. 2015, 11, 1781–1785, doi:10.3762/bjoc.11.193

• pathway [17][20], or a Suzuki–Miyaura cross-coupling reaction [21]. The use of triazine derivatives (which under particular conditions undergo an inverse Diels–Alder reaction) can also produce oligopyridines [22]. On the other hand, there are a limited number of reports dealing with the preparation of

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

• . Starting from aniline derivative 1b, a one pot diazotization–borylation sequence using different acids afforded the corresponding borylated product 2b in good yields (Table 3). Suzuki–Miyaura cross-coupling reactions of boronates 2a and 2b with aryl iodides using a simple system without any optimization

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

• –Miyaura coupling: Bodwell and Li [127] have reported the synthesis of the cyclophane 130 involving hydroboration and the Suzuki–Miyaura (SM) coupling [128][129][130][131][132][133][134][135] as key steps. 1,3-Diallylindole (127) was first synthesized in two steps from indole (123) by successive allylation

• N-allylation afforded 125 (98%). The treatment of compound 125 with n-BuLi followed by alkylation with allyl bromide gave diallylindole 127 (77%), which on further treatment with 9-BBN (6 equiv) gave the doubly hydroborated species 128. Then, it was directly subjected to the Suzuki–Miyaura coupling

• reaction with 3,6-diiodopyridazine (129) and the desired cyclophane 130 was obtained (30%) as an oil (Scheme 18). In 2012, Hutton and co-workers [136] have synthesized a highly strained bicyclic framework of mycocyclosin (135) by utilizing the intramolecular Suzuki–Miyaura [137] cross-coupling reaction as

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells

• Gleb Sorohhov,
• Chenyi Yi,
• Michael Grätzel,
• Silvio Decurtins and
• Shi-Xia Liu

Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118

• , the synthesis of the key intermediate 7 involves the protection of one aldehyde group as an acetal using pinacol prior to HWE reaction of 5 with 4,5-bis(hexylthio)-1,3-dithiole-2-thione, followed by deprotection under acidic conditions. Aldehyde 5 was readily obtained by palladium-catalyzed Suzuki

• –Miyaura coupling reaction between 4,4,5,5-tetramethyl-2-(4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)phenyl)-1,3,2-dioxaborolane and 6-bromo-4,4-dihexyl-4H-cyclopenta[2,1-b:3,4-b’]dithiophene-2-carbaldehyde [23]. All these new precursors and the two target dyes 1 and 2 were purified by chromatography and

Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

• Masashi Hasegawa,
• Junta Endo,
• Seiya Iwata,
• Toshiaki Shimasaki and
• Yasuhiro Mazaki

Beilstein J. Org. Chem. 2015, 11, 972–979, doi:10.3762/bjoc.11.109

• . Previously, a racemic conjugated polymer in the literature was prepared by a Suzuki–Miyaura or Yamamoto coupling reaction from (rac)-8 [17]. In contrast, to the best of our knowledge, there is no example of a chiral polymer based on the 1,3-diphenylallene frameworks that can be a unit of copolymer with

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

• ability to transmetallation, to coordinate to the organoboronic acid with the three-coordinated boron atom to ArPdL2OH and subsequent transmetallation (Scheme 1). However, some experimental facts indicate the multilateral role of silver(I) compounds AgmY in the acceleration of the Suzuki–Miyaura cross

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

• 58030, tel.: +52 443 326 5790; fax: +52 443 326 5788 10.3762/bjoc.10.299 Abstract A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II), was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under

• ]. The palladium-catalyzed cross-coupling of arylboronic acid and aryl halides in the Suzuki–Miyaura (SM) reaction is one of the most popular and important methods to obtain biaryls, which are essential structures of many important compounds such as natural products [7], agrochemicals [8

• ppm, with its integration indicating one proton. This result suggests to us that the palladium interacts with the carbonyl and amine groups of the pyrazole ring of 4-AAP. The synthesized 4-AAP–Pd(II) complex was used to carry out all palladium-catalyzed Suzuki–Miyaura cross-coupling reactions

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• synthesise 6. Whereas the synthesis of 6 was achieved in 33% yield, the yield decreased to 12% when the derivative with two thiophenes was prepared [47]. The BODIPY-DPP-BODIPY triads (9 and 10) were synthesised via Suzuki–Miyaura cross-coupling by reaction of the functionalised DPP core 8 [48] with the

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• , Buchwald and Hartwig on the use of monophosphine ligands in cross-coupling reactions, notably carbon–carbon ones such as the Mizoroki–Heck [1][2][3] and Suzuki–Miyaura reactions [4][5][6], there is a renewed interest for tertiary phosphines that favour the formation of singly phosphorus-ligated complexes

P(O)R₂-directed Pd-catalyzed C–H functionalization of biaryl derivatives to synthesize chiral phosphorous ligands

• Rong-Bin Hu,
• Hong-Li Wang,
• Hong-Yu Zhang,
• Heng Zhang,
• Yan-Na Ma and
• Shang-dong Yang

Beilstein J. Org. Chem. 2014, 10, 2071–2076, doi:10.3762/bjoc.10.215

• reported operation, the substrates of biaryl derivatives that contained phosphate with axial chirality were obtained in high yields using the Suzuki–Miyaura coupling reaction with the assistance of this versatile chiral ligand [31][32][33][34]. We used substituted naphthylboronic acid or ortho-substituted

• were successfully synthesized using the Suzuki–Miyaura coupling reaction under the assistance of a chiral ligand. Moreover, the substrates were further C–H functionalized using the P(O)Ar2 directing role with Pd salt as catalyst. Notably, the reactions took place in air atmosphere and at high

Aryl substitution of pentacenes

• Andreas R. Waterloo,
• Anna-Chiara Sale,
• Dan Lehnherr,
• Frank Hampel and
• Rik R. Tykwinski

Beilstein J. Org. Chem. 2014, 10, 1692–1705, doi:10.3762/bjoc.10.178

• opportunity to vary the pendent substituent through a Pd-catalyzed cross-coupling protocol (Scheme 2). Thus, pentacene 3g was treated under Suzuki–Miyaura coupling conditions with arylboronic acids, and the desired pentacenes 3j,k were obtained in yields of 92 and 68%, respectively. Notably, anthracenyl

• nucleophilic addition (yields given are for the pentacene product 3, over the two steps from either 4a or 4b). Functionalization of iodoaryl pentacene 3g using the Suzuki–Miyaura cross-coupling reaction. Optical properties of pentacenes 3a–k, unsubstituted pentacene (PEN), and TIPSPc. Thermal properties of a

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• reaction produced the arylstannane in 75 to 90% yield [88]. The Suzuki–Miyaura cross-coupling reaction is another type of reaction with the phosphate group acting as a leaving group. As exemplified in Scheme 30, the aryl dialkyl phosphate was produced in good yield by an AT reaction [89]. Then, this

4-Hydroxy-6-alkyl-2-pyrones as nucleophilic coupling partners in Mitsunobu reactions and oxa-Michael additions

• Michael J. Burns,
• Thomas O. Ronson,
• Richard J. K. Taylor and
• Ian J. S. Fairlamb

Beilstein J. Org. Chem. 2014, 10, 1159–1165, doi:10.3762/bjoc.10.116

• could find only limited precedent for this procedure being used previously in this way [15][16][17]. In our case, we were able to further modify the resulting pyronyl ether forming a trisubstituted enol ether, which then underwent a Suzuki–Miyaura cross-coupling or direct arylation-type reaction. As

Palladium-catalysed cross-coupling reaction of ultra-stabilised 2-aryl-1,3-dihydro-1H-benzo[d]1,3,2-diazaborole compounds with aryl bromides: A direct protocol for the preparation of unsymmetrical biaryls

• Siphamandla Sithebe and
• Ross S. Robinson

Beilstein J. Org. Chem. 2014, 10, 1107–1113, doi:10.3762/bjoc.10.109

• absorption and fluorescence characteristics. Here we describe the first palladium-catalysed Suzuki–Miyaura cross-coupling reaction of easily accessible and ultra-stabilised 2-aryl-1,3-dihydro-1H-benzo[d]1,3,2-diazaborole derivatives with various aryl bromides. Aryl bromides bearing electron-withdrawing

• , electron-neutral and electron-donating substituents are reacted under the catalytic system furnishing unsymmetrical biaryl products in isolated yields of up to 96% in only 10 minutes. Keywords: aryl bromide; 2-aryl-1,3-dihydro-1H-benzo[d]1,3,2-diazaborole; asymmetrical biaryls; microwave; Suzuki–Miyaura

• [1][2][3][4][5]. Amongst them, the Suzuki–Miyaura cross-coupling reaction of aryl halides/triflates and organoboron compounds is one of the most documented and versatile cross-coupling reaction in the literature [6]. The use of organoboron compounds 1, 2 and 3 (Figure 1) as nucleophilic coupling