Structure–property relationships and third-order nonlinearities in diketopyrrolopyrrole based D–π–A–π–D molecules

• Jan Podlesný,
• Lenka Dokládalová,
• Oldřich Pytela,
• Adam Urbanec,
• Milan Klikar,
• Numan Almonasy,
• Tomáš Mikysek,
• Jaroslav Jedryka,
• Iwan V. Kityk and
• Filip Bureš

Beilstein J. Org. Chem. 2017, 13, 2374–2384, doi:10.3762/bjoc.13.235

• boron derivatives [34][35]. Twofold Sonogashira cross-coupling was utilized towards chromophores 1b–5b. All cross-coupling reactions were carried out in THF with PdCl2(PPh3)2 as palladium precatalyst. The reaction time was approximately 24 hours to achieve sufficient conversion (32–73%). Despite bearing

• in modular way prepared by Suzuki–Miyaura, Migita–Stille, and Sonogashira cross-coupling reactions. The chromophores differ in the π-system extension as well as in the peripheral substitution. The thermal stability of 1–5 is mostly affected by the presence of acetylene linkers, 1,4-phenylene and 2,5

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• under Sonogashira cross-coupling conditions (Scheme 6). UV–vis absorption measurements suggested that the deoxyribonucleoside-linked TFEO-Pcs had a non-aggregation property, as expected. Unfortunately, it was also found that these conjugates gradually decomposed under light irradiation, so their

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Aggregation behaviour of a single-chain, phenylene-modified bolalipid and its miscibility with classical phospholipids

• Simon Drescher,
• Vasil M. Garamus,
• Christopher J. Garvey,
• Annette Meister and
• Alfred Blume

Beilstein J. Org. Chem. 2017, 13, 995–1007, doi:10.3762/bjoc.13.99

• -Mothes-Str. 3, 06120 Halle (Saale), Germany 10.3762/bjoc.13.99 Abstract In the present work, we describe the synthesis of a single-chain, phenylene-modified bolalipid with two phosphocholine headgroups, PC-C18pPhC18-PC, using a Sonogashira cross-coupling reaction as a key step. The aggregation behaviour

• synthesised from the corresponding diol (HO-C18pPhC18-OH) by established phosphorylation and quarternisation reactions described previously [38]. The long-chain, phenylene-modified 1,ω-diol in turn was prepared using a bis-Sonogashira cross-coupling reaction [37] with PdCl2(PPh3)2 as catalyst and tetra-n

Transition-metal-free one-pot synthesis of alkynyl selenides from terminal alkynes under aerobic and sustainable conditions

• Adrián A. Heredia and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2017, 13, 910–918, doi:10.3762/bjoc.13.92

• synthesis of seleno-functionalized heterocycles [20][21]. Recently, the use of alkynyl selenides as substrates for Pd-catalyzed Suzuki, Negishi, Kumada and Sonogashira cross-coupling reactions has been reported with good yields [22]. Due to the synthetic relevance of alkynyl selenides several methodologies

First total synthesis of kipukasin A

• Chuang Li,
• Haixin Ding,
• Zhizhong Ruan,
• Yirong Zhou and
• Qiang Xiao

Beilstein J. Org. Chem. 2017, 13, 855–862, doi:10.3762/bjoc.13.86

• Sonogashira cross-coupling with 1-hexyne provided ribose 14 in 78% yield [35]. Subsequently, using DMAP as acylation catalyst and triethylamine as base, the former synthesized 2,4-dimethoxy-6-methylbenzoyl chloride (9) reacted with ribose 14 to 3-O-(2,4-dimethoxy-6-methylbenzoyl)ribose 15 in 74% yield

A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

• Xiao Huang,
• Li Yang,
• Rikard Emanuelsson,
• Jonas Bergquist,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 2682–2688, doi:10.3762/bjoc.12.265

• of such functionalization using a Sonogashira cross-coupling [26] and an azide–alkyne Huisgen cycloaddition [27]. One of the advantages of the cross-coupling and click chemistry is that it allows for reaction conditions tolerant for nearly all of the above mentioned functional groups. Additionally

• present EDOT functionalization routes. The synthetic route from glycidol to pyEDOT (3). The synthetic route from D-mannitol diketal to eEDOT 8 and TMS-eEDOT 8’. New EDOT derivatives 9–13 accessible from pyEDOT with bromo-pendant group precursors via Sonogashira cross coupling and with an azide pendant

The direct oxidative diene cyclization and related reactions in natural product synthesis

• Juliane Adrian,
• Leona J. Gross and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2016, 12, 2104–2123, doi:10.3762/bjoc.12.200

• oxidative cyclization catalyzed by Ru(VII) yielded THF diol 102 in 55% yield as a single diastereoisomer, without considering the configuration of the protected alcohol, as this position was subsequently oxidized to enable a Sonogashira cross-coupling to access 103. The tricyclic core structure 104 could be

Scope and limitations of a DMF bio-alternative within Sonogashira cross-coupling and Cacchi-type annulation

• Kirsty L. Wilson,
• Alan R. Kennedy,
• Jane Murray,
• Ben Greatrex,
• Craig Jamieson and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2016, 12, 2005–2011, doi:10.3762/bjoc.12.187

• solvents; however, despite their utility, these solvents are incompatible with the drive towards more sustainable chemical synthesis. Herein, we describe the scope and limitations of an alternative to DMF derived from renewable sources (CyreneTM) in Sonogashira cross-coupling and Cacchi-type annulations

• ][43], with an emphasis on scope and limitations of its application. Results and Discussion To explore the use of Cyrene in the context of the Sonogashira cross-coupling, we established a simple benchmark reaction using iodobenzene (1a) and phenylacetylene (2a) (Table 1). A typical literature-derived

• comparison with standard solvents (THF and DMF; Table 1, entries 9 and 10, respectively). Continuing with the primary investigation and with an optimised set of reaction conditions, we sought to explore the generality of Cyrene in the Sonogashira cross-coupling (Scheme 2). Significantly, a broad range of

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• -configuration were formed by SmI2-mediated reductive dimerization of a 4-(indol-6-yl)butenone, obtained by Heck reaction. The two indolyl units appear to chelate Sm(II)/(III) leading to a gauche-type arrangement at the newly formed bond between the two β-carbons. Through a sequence of Sonogashira cross coupling

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

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing

• Bradley D. Rose,
• Peter J. Santa Maria,
• Aaron G. Fix,
• Chris L. Vonnegut,
• Lev N. Zakharov,
• Sean R. Parkin and
• Michael M. Haley

Beilstein J. Org. Chem. 2014, 10, 2122–2130, doi:10.3762/bjoc.10.219

• dramatically alter the intermolecular electronic coupling, which is what ultimately dictates performance of the device [18][19]. Results and Discussion Synthesis. Our initial studies [20] toward 8 (Scheme 1) focused on the Sonogashira cross-coupling of known diiodo intermediate 9, which was prepared by double

• . Black lines represent the molecules with circles denoting the centroid. Transannular cyclization route to diethynyl-IF-diones 8. Suzuki/Friedel-Crafts route to diethynyl-IF-diones 8. Diethynyl-IF-diones synthesized and yields for Sonogashira cross-coupling. Electrochemical and optical data for ID-diones

• Kitamura gave tetrahalide 12 in good yield on >10 g scale [25]. Suzuki cross-coupling with 12 furnished p-terphenyl 14, followed by oxidation of the methyl groups to produce diacid 15. Intramolecular Friedel–Crafts acylation then afforded 5,11-dibromo-IF-dione 11. The yields for the Sonogashira cross

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

Molecular recognition of isomeric protonated amino acid esters monitored by ESI-mass spectrometry

• Andrea Liesenfeld and
• Arne Lützen

Beilstein J. Org. Chem. 2014, 10, 825–831, doi:10.3762/bjoc.10.78

• , followed by hydrolysis to afford phenol 6 which was finally transferred into the corresponding triflate 7 in 64% yield (Scheme 1). Triflate 7 was then subjected to a Sonogashira cross-coupling reaction and a Suzuki cross-coupling reaction followed by treatment with boron tribromide to obtain the

Synthesis of 3,4-dihydro-1,8-naphthyridin-2(1H)-ones via microwave-activated inverse electron-demand Diels–Alder reactions

• Salah Fadel,
• Youssef Hajbi,
• Mostafa Khouili,
• Said Lazar,
• Franck Suzenet and
• Gérald Guillaumet

Beilstein J. Org. Chem. 2014, 10, 282–286, doi:10.3762/bjoc.10.24

• electron-demand Diels–Alder reaction from 1,2,4-triazines bearing an acylamino group with a terminal alkyne side chain. Alkynes were first subjected to the Sonogashira cross-coupling reaction with aryl halides, the product of which then underwent an intramolecular inverse electron-demand Diels–Alder

• reaction to yield 5-aryl-3,4-dihydro-1,8-naphthyridin-2(1H)-ones by an efficient synthetic route. Keywords: inverse-electron-demand Diels–Alder reaction; microwave irradiation; naphthyridin-2(1H)-ones; Sonogashira cross-coupling; 1,2,4-triazine; Introduction 1,8-Naphthyridine derivatives are an important

• envisaged to evaluate the reactivity of internal alkynes towards the inverse electron-demand Diels–Alder reaction. To reach this goal, we decided to functionalize the alkynes 6–9 employing the Sonogashira cross-coupling reaction. Preparation of aryl-N-triazinylpentynamides The terminal alkynes 6–9 were then

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II) complexes

• Amaresh Mishra,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2013, 9, 866–876, doi:10.3762/bjoc.9.100

• Amaresh Mishra Elena Mena-Osteritz Peter Bauerle Institute of Organic Chemistry II and Advanced Materials, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany 10.3762/bjoc.9.100 Abstract Pd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated

• Syntheses. A modular approach was selected for the synthesis of the targeted metallodendrimers, consisting of (1) the preparation of dendrons by employing Sonogashira cross-coupling reactions, (2) their functionalization with tpy-ligands, and (3) formation of the corresponding homoleptic Ru(II) complexes

Dipyrazolo[1,5-a:4',3'-c]pyridines – a new heterocyclic system accessed via multicomponent reaction

• Wolfgang Holzer,
• Gytė Vilkauskaitė,
• Eglė Arbačiauskienė and
• Algirdas Šačkus

Beilstein J. Org. Chem. 2012, 8, 2223–2229, doi:10.3762/bjoc.8.251

• formylation (with concomitant transformation of the oxygen into a chlorine substituent), followed by Sonogashira cross-coupling reaction of the obtained 5-chloropyrazole-4-carbaldehydes with appropriate alkynes, has been described by us in a former publication [21]. Compounds 1 containing an alkyne function

Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes

• Tsutomu Konno,
• Misato Kishi and
• Takashi Ishihara

Beilstein J. Org. Chem. 2012, 8, 2207–2213, doi:10.3762/bjoc.8.249

• in situ generated vinylcuprates could react very smoothly with an excess amount of iodine, the vinyl iodides being obtained in high yields. Thus-obtained iodides underwent a very smooth Sonogashira cross-coupling reaction to afford various trans-enediynes in high yields. Keywords: carbocupration

• PPh3 and CuI in DMF at room temperature for 24 h, gave the corresponding Sonogashira cross-coupling products 3a–e in good to high yields [24][25][26] (Scheme 2). Subsequently, 3a was subjected to the usual β-elimination conditions according to the literature [23][27][28][29], i.e., treatment of 3a with

• stereoselective manner. Finally, we attempted the Sonogashira cross-coupling reaction of the obtained iodide 13a (Scheme 4). Thus, treatment of 13a with 1.2 equiv of terminal alkynes and 40 equiv of Et3N in the presence of 10 mol % each of Pd(PPh3)4 and CuI in THF at 70 °C for 2–5 h gave the corresponding

Synthesis of multivalent host and guest molecules for the construction of multithreaded diamide pseudorotaxanes

• Nora L. Löw,
• Egor V. Dzyuba,
• Boris Brusilowskij,
• Lena Kaufmann,
• Elisa Franzmann,
• Wolfgang Maison,
• Emily Brandt,
• Daniel Aicher,
• Arno Wiehe and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2012, 8, 234–245, doi:10.3762/bjoc.8.24

• Berlin, Germany 10.3762/bjoc.8.24 Abstract A series of di-, tri- and tetravalent axles and wheels for the synthesis of pseudorotaxanes bearing the tetralactam macrocycle/diamide axle binding motif was prepared. Starting from iodinated monovalent precursors, Sonogashira cross-coupling reactions were

• (wheel)N–H···O=C(axle) hydrogen bonds. Through the iodine substituents, both building blocks can be connected to appropriate spacers in Sonogashira cross-coupling reactions [102]. This coupling strategy creates rather rigid connections to the spacers and helps in reducing the entropic penalties that

• Discussion Synthesis of monovalent precursors Although aryl bromides, triflates and sometimes even chlorides react efficiently in Sonogashira cross-coupling reactions, our previous studies [103][104] showed that only the iodinated TLM, and in some rare cases the corresponding triflate-substituted wheel, is

Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

• Jiří Kulhánek and
• Filip Bureš

Beilstein J. Org. Chem. 2012, 8, 25–49, doi:10.3762/bjoc.8.4

• chromophores 95–100 (Figure 18; [112]). The synthesis of this series of chromophores involved two-fold Suzuki–Miyaura and Sonogashira cross-coupling reactions on dibromoolefin 94 (for X-ray structure see [113]). This compound proved to be a very useful, fully planar precursor for the construction of a

Impact of the level of complexity in self-sorting: Fabrication of a supramolecular scalene triangle

• Kingsuk Mahata and
• Michael Schmittel

Beilstein J. Org. Chem. 2011, 7, 1555–1561, doi:10.3762/bjoc.7.183

• ] (Figure 1). The coordination behaviour of molecular component 3 was integrated into 5, the latter being synthesised in a Sonogashira homocoupling reaction [27]. The information stored in 1 and 4 was instated in the unsymmetrical bisphenanthroline 6, readily accessible by stepwise Sonogashira cross

• -coupling reactions [15]. A known procedure was followed to prepare the terpyridine–phenanthroline hybrid 7 [8]. The lengths of the ligands were chosen in such a way that they provide the geometrically different sides of a scalene triangle. Results and Discussion We tested both self-sorting algorithms as

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

• ,β-unsaturated ketones generated in situ by Pd-catalyzed Sonogashira cross-coupling reactions. For instance, by building on their expertise in this area [14] Müller and coworkers recently developed a very effective and modular three-component strategy to assemble a series of 3,5-bis(hetero)aromatic

• are formed, they immediately react with hydrazine to form pyrazole by a specific rate acceleration in the one-pot process [16]. The Sonogashira cross-coupling of acid chlorides with terminal alkynes has also been demonstrated as a valuable tool to generate, in situ, ynones bearing a pendant amine

• –N allylic amination, followed by a Sonogashira cross-coupling and an intramolecular hydroamination furnished a dihydroexoalkylidene pyrrole 55, which rearranges into pyrrole 56. This Pd/Cu-mediated three-component approach is influenced by the nature of the nitrogen nucleophile, and the reaction

Asymmetric Au-catalyzed cycloisomerization of 1,6-enynes: An entry to bicyclo[4.1.0]heptene

• Alexandre Pradal,
• Chung-Meng Chao,
• Patrick Y. Toullec and
• Véronique Michelet

Beilstein J. Org. Chem. 2011, 7, 1021–1029, doi:10.3762/bjoc.7.116

• studies. Synthesis of 1,6-enynes We prepared various oxygen-tethered 1,6-enynes according to classic methodologies employing a Williamson alkylation reaction and/or a Sonogashira cross-coupling [60][61] (Scheme 2 and Scheme 3). The known enyne 5 [62][63] was engaged in Pd-catalyzed coupling in the

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

• Deyun Qian and
• Junliang Zhang

Beilstein J. Org. Chem. 2011, 7, 808–812, doi:10.3762/bjoc.7.92

• , Chinese Academy of Sciences, Ling Ling Road 345 Shanghai 200032 (P. R. China) 10.3762/bjoc.7.92 Abstract A straightforward, efficient, and reliable redox catalyst system for the Au(I)/Au(III)-catalyzed Sonogashira cross-coupling reaction of functionalized terminal alkynes with arylboronic acids under

• mild conditions has been developed. Keywords: arylboronic acid; gold-catalysis; Sonogashira cross-coupling; Introduction The Sonogashira reaction has become the most important and widely used method for the synthesis of arylalkynes and conjugated enynes, which are precursors for natural products

• cross-coupling, as well as expanding the substrate scope [11][12][13][14]. Various examples have recently been reported for the palladium-catalyzed Sonagashira-type cross-coupling of terminal alkynes with arylboronic acids [13], and the Pd(0)/Pd(II) catalytic cycles have been well studied. Nevertheless