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

• similar reaction conditions gave the cyclized product 8-exo-69 (30%) as the only isolable compound (Scheme 10). Kumada coupling: Weber and co-workers [98] have synthesized muscopyridine 73 starting from 2,6-disubstituted pyridine. The Kumada cross-coupling reaction of 2,6-dichloropyridine (70) with the

• ) using the McMurry coupling (Figure 8). Pd(0)-catalyzed cross-coupling reaction: In 1997, Yamamoto and co-workers [122] have synthesized the exomethylene paracyclophane 108 via intramolecular benzannulation of conjugated enynes in the presence of palladium(0). In this regard, dibromoalkane 103 was

• 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

Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

• Jerzy Zakrzewski and
• Bogumiła Huras

Beilstein J. Org. Chem. 2015, 11, 1155–1162, doi:10.3762/bjoc.11.130

• Mizoroki–Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. Keywords: 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1

• -oxyl; cinnamates; Mizoroki–Heck cross-coupling reaction; nitroxides; Introduction Cinnamic acid derivatives are known as biologically active compounds. Cinnamic acid and its hydroxy derivatives bearing a phenolic moiety such as coumaric, caffeic, ferulic, sinapinic, and chlorogenic acids [2][3][4][5

• been obtained using the Mizoroki–Heck cross-coupling reaction between aryl halides and an olefin [7][13][14][15][16][17]. Because cinnamates themselves are also olefins, they can serve as cinnamic substrates to synthesize more complex cinnamates [18][19]. Cinnamic acid derivatives are also formed when

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

• ethoxyphosphoryl groups (12) in 63% yield. We adopted the cross-coupling reaction between the 1,3-dithiole-2-thione and the 1,3-dithiol-2-one derivatives for the following reasons. The homo-coupling reaction of 10 afforded 12 in low yields, and purification by column chromatography was difficult because of

• undesired byproducts. The homo-coupling reaction using 11 might give 12 in a good yield, however, toxic and expensive mercury(II) acetate has to be used for the synthesis of 11. Thus, the cross-coupling reaction is useful for saving 11. The Horner–Wadsworth–Emmons reaction of 12 with 2 equiv of aldehydes

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• silica gel chromatography. We should note that an increase of temperature resulted in the degradation of starting material 6. This first strategy to reach clips 1 and 2 was considering the trimethylphosphite-mediated cross-coupling reaction involving 2-oxo-1,3-dithiole moiety 8 [28] as an efficient route

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

• . Furthermore, the first synthesis of a chiral copolymer containing TTFs based on a chiral allenic framework (poly-3: PTDPA is also demonstrated. Results and Discussion To anchor the TTF groups into the allene framework, we chose a cross-coupling reaction of unknown 1,3-bis(4-iodophenyl)-1,3-diisopropylallene

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• -tetrathiafulvalene (CNB-EDT-TTF), was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic

• report here a new non-symmetrically substituted TTF donor with one dithiin ring and one cyanobenzene ring obtained by a cross coupling reaction. These two rings are expected to enhance the degree of π-delocalization over the molecule when compared with simple TTF, while the presence of the nitrogen atom

• pyrazine groups substituted TTFs recently reported by our group [13][22][23]. Conclusion In conclusion, we have prepared in fair yield a new non-symmetrically substituted cyanobenzene TTF-type electron donor, CNB-EDT-TTF, by a cross coupling reaction followed by chromatographic separation. The crystal

Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

• Sultan Taskaya,
• Nurettin Menges and
• Metin Balci

Beilstein J. Org. Chem. 2015, 11, 897–905, doi:10.3762/bjoc.11.101

• and N-propargylindole-2-carboxylic acids 37, 41 and 45, which were synthesized by hydrolysis of the corresponding esters (Table 2). The Sonogashira cross-coupling reaction [56][57][58][59][60][61] was used for the synthesis of the desired starting materials 29 and 33. For the Sonogashira coupling

Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks

• Mirko Lohse,
• Larissa K. S. von Krbek,
• Sebastian Radunz,
• Suresh Moorthy,
• Christoph A. Schalley and
• Stefan Hecht

Beilstein J. Org. Chem. 2015, 11, 748–762, doi:10.3762/bjoc.11.85

• benzylamine yielding amine 10, which was subsequently Boc-protected, then reacted with trimethylsilylacetylene in a Sonogashira cross-coupling followed by desilylation. Finally, the porphyrin cores 1 and 2 were combined with axle precursor 8 in another two and four-fold Sonogashira cross-coupling reaction

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• MeOH gives the corresponding primary amide 7 in 63% yield. Its dehydration with POCl3 in sulfolane gives 2ac in 60% yield. A similar phosphite-based cross-coupling reaction between the bis(trifluoromethyl)-1,3-dithiole-2-one derivative 9cc and the diester derivative 10bb gave the TTF 3bc in 15% yield

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

• continuation of systematic research of the Suzuki–Miyaura cross-coupling reaction of weakly nucleophilic organotrifluoroborates we report here the study of the relative reactivity of K[4-RC6F4BF3] in the Pd-catalyzed reactions with some aryl bromides and iodides in the presence of Ag2O. The borates were chosen

• . The assumed silver(I) oxide assisted transmetallation with organoboronic acids. Cross-coupling of K[4-RC6F4BF3] (1a–r) with 3-IC6H4F (2) and 4-IC6H4F (3). Attempted synthesis of 7 (3’-F) and 8 (4’-F) by cross-coupling reaction. Synthesis of biphenyls 10a,c–f,h–p. Pd-catalyzed cross-coupling of 1a and

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• stereochemical integrity. Scheme 12 shows an example of this cross-coupling reaction. So far, there are not many examples of copper-catalyzed ECA reactions of α,β-unsaturated amides and lactams. One limitation to the methodology that has already been reported is that 1,4-addition of carbon nucleophiles to

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

• Roberto Blanco Trillo,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2015, 11, 313–322, doi:10.3762/bjoc.11.36

• intramolecular palladium-catalyzed alkyl–aryl cross-coupling reaction [13] and in Pd-catalyzed allylic substitutions [14]. Several of the highly sterically hindered BIFOP derivatives were employed as ligands in Cu-catalyzed 1,4-additions [15]. Similar chelating fencholates [16][17][18][19][20][21][22] (Scheme 1

Sequential decarboxylative azide–alkyne cycloaddition and dehydrogenative coupling reactions: one-pot synthesis of polycyclic fused triazoles

• Kuppusamy Bharathimohan,
• Thanasekaran Ponpandian,
• A. Jafar Ahamed and
• Nattamai Bhuvanesh

Beilstein J. Org. Chem. 2014, 10, 3031–3037, doi:10.3762/bjoc.10.321

• ][30][31][32][33]. The double C–H activation (dehydrogenative cross coupling) reaction can be classified into two categories: intermolecular and intramolecular. There are several reports in literature describing intermolecular sp2 C–H/C–H coupling reactions [24][25][26][27][28][29][30][31][32][33

• followed by C–H functionalization (Scheme 1). Specifically, they demonstrated a C–H functionalization of an indole nucleus with 5-iodo-1,2,3-triazoles. In the present study, we replaced the 5-iodo-1,2,3-triazoles with 5H-1,2,3-triazoles with intramolecular sp2 C–H/C–H cross coupling reaction. To the best

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

• mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II) as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups

• their rapid transmetalation with palladium(II) complexes [11]. Although in recent years there have been numerous studies on the SM cross-coupling reaction, the necessity for a simple procedure that allows the formation of C–C bonds in functionalized substrates remains. There have been ongoing efforts to

• , we report the synthesis of the new 4-aminoantipyrine–Pd(II) complex [4-AAP–Pd(II)] by mixing Li2PdCl4, 4-aminoantipyrine in presence of NaOAc in MeOH at room temperature, and its performance as catalysts in SM cross-coupling reaction of structurally different aryl halides with phenylboronic acids

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

• Jun Terao,
• Yohei Konoshima,
• Akitoshi Matono,
• Hiroshi Masai,
• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297

• ]rotaxane by a cross-coupling or complexation reaction of thus formed pseudo linked [3]rotaxane. Oligo(para-phenylene), oligothiophene, and porphyrin derivatives were used as π-conjugated guests with stopper groups. Keywords: cross-coupling reaction; insulated π-conjugated molecule; oligothiophene

• shorter than the depth of PMCD, the cross-coupling reaction is strongly inhibited because the reaction has to occur in the PMCD cavity (Figure 1a). On the other hand, a self-inclusion complex does not form if the guest is longer than the internal diameter of PMCD (Figure 1c). Thus far, we have succeeded

• linked [3]rotaxane precursor with a 5,15-di([1,1'-biphenyl]-4-yl)porphyrin backbone as the guest unit is shown in Scheme 1. In order to fix the pseudo [3]rotaxane structure, we introduced two bromo groups (cross-coupling reaction point) at both terminal positions of the 5,15-di([1,1'-biphenyl]-4-yl

Synthesis of 2-trifluoromethylpyrazolo[5,1-a]isoquinolines via silver triflate-catalyzed or electrophile-mediated one-pot tandem reaction

• Xiaoli Zhou,
• Meiling Liu,
• Puying Luo,
• Yingjun Lai,
• Tangtao Yang and
• Qiuping Ding

Beilstein J. Org. Chem. 2014, 10, 2286–2292, doi:10.3762/bjoc.10.238

• -coupling reaction. Conclusion In conclusion, we have developed an efficient one-pot tandem cyclization/[3 + 2] cycloaddition reaction of N’-(2-alkynylbenzylidene)hydrazides with ethyl 4,4,4-trifluorobut-2-ynoate under silver triflate-catalyzed or electrophiles-mediated conditions. Highly functionalized

• 13C NMR, HRMS, as well as X-ray diffraction analysis (Figure 1, for details, see Supporting Information File 1). Based on this one-pot tandem electrophilic cyclization/[3 + 2] cycloaddition reactions, highly functionalized pyrazolo[5,1-a]isoquinolines can be obtained via palladium-catalyzed cross

Synthesis of trifluoromethyl-substituted pyrazolo[4,3-c]pyridines – sequential versus multicomponent reaction approach

• Barbara Palka,
• Angela Di Capua,
• Maurizio Anzini,
• Gyté Vilkauskaité,
• Algirdas Šačkus and
• Wolfgang Holzer

Beilstein J. Org. Chem. 2014, 10, 1759–1764, doi:10.3762/bjoc.10.183

• pyrazole precursor. Employing the latter approach we recently presented a novel method for the synthesis of the pyrazolo[4,3-c]pyridine system by Sonogashira-type cross-coupling reaction of easily obtainable 5-chloro-1-phenyl-1H-pyrazole-4-carbaldehydes with various alkynes and subsequent ring-closure

Synthesis of rigid p-terphenyl-linked carbohydrate mimetics

• Maja Kandziora and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 1749–1758, doi:10.3762/bjoc.10.182

• bicyclic 1,2-oxazine derivative 3 was used as key building block for the Suzuki cross-coupling reaction to synthesize p-terphenyl-linked derivatives 1. The key intermediate 3 was prepared by a Lewis acid-induced rearrangement of 3,6-dihydro-2H-oxazine 4, that origins from a stereoselective [3 + 3

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

• 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

Synthesis, characterization and DNA interaction studies of new triptycene derivatives

• Sourav Chakraborty,
• Snehasish Mondal,
• Rina Kumari,
• Sourav Bhowmick,
• Prolay Das and
• Neeladri Das

Beilstein J. Org. Chem. 2014, 10, 1290–1298, doi:10.3762/bjoc.10.130

• tribromotriptycenes as synthons [36], syntheses of triethynyltriptycenes (TETs) 1 and 2 were efficiently realized in two steps (Scheme 1). In the presence of Pd(0) catalyst and cuprous iodide (cocatalyst), Sonogashira cross-coupling reaction of 2,6,14-tribromotriptycene with 3.0 equiv of (trimethylsilyl)acetylene in

Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp²)–H activation/C–O formation

• Seohyun Shin,
• Dongjin Kang,
• Woo Hyung Jeon and
• Phil Ho Lee

Beilstein J. Org. Chem. 2014, 10, 1220–1227, doi:10.3762/bjoc.10.120

• , the tolerance of the chloro groups may be of importance for a subsequent catalytic cross-coupling reaction. Substrate 1n, which contains a 2-thiophenyl moiety, was subjected to the cyclization affording 2n in 52% yield. The preparation of 2-arylphenylphosphonic acid monoethyl esters with a nitro

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

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

• [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

• partners in the Suzuki–Miyaura cross-coupling reaction is particularly attractive due to the non-toxicity of the byproducts, the ease with which they are transmetalated and their high stability towards air and moisture, which are the key features for coupling reactions [7]. On one hand, structural diverse

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

• easily be derived from the corresponding ketone and they are more reactive then the vinyl chloride or bromide during the oxidative addition. More recently also vinyl tosylates and enol phosphates have proven to be suitable reagents. The catalytic arylic C–P cross-coupling reaction can be a greener

• temperature when the vinyl tosylate was substituted with an electron-withdrawing group like in 85 (Scheme 22). The group of Gaumont has also reported their preliminary results for the enantioselective palladium-catalyzed C–P cross-coupling reaction between an achiral vinyl triflate 80c and a racemic secondary

• -coupling reaction (Scheme 24) [166]. The enol phosphates 88 were prepared from the corresponding amides. The phosphane function was introduced in the α-position of the nitrogen. Several chiral and achiral secondary phosphine borane complexes 13 were used. The coupling was achieved under mild conditions

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

• Affording valued biaryls and heterobiaryls, namely ubiquitous chemical moieties in pharmaceuticals, natural products, photoactive species and many other functional molecules, the Suzuki–Miyaura cross-coupling reaction is widely employed by the fine chemicals and pharmaceutical industries [1]. The reaction