Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• -unsaturated ester 42. Conversion of the installed alkene to the corresponding thioether followed by the reduction of the ester moiety using DIBAL gave the compound 43, which was subjected to a Stille coupling reaction [38] to yield compound 45. Hydrogenation reaction in the presence of metallic Mg [39

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• (dba)3, SPhos, and Et3N in 86% yield. Reduction of the double bond with Pd/C followed by dual Stille coupling for the introduction of two methyl groups and Mukaiyama hydration utilizing Mn(dpm)3 and PhSiH3 furnished the misassigned structure for dysiherbol A (79). A revised structure was finally

Synthesis, optical and electrochemical properties of (D–π)₂-type and (D–π)₂Ph-type fluorescent dyes

• Kosuke Takemura,
• Kazuki Ohira,
• Taiki Higashino,
• Keiichi Imato and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2022, 18, 1047–1054, doi:10.3762/bjoc.18.106

• with two (diphenylamino)carbazole-thiophene units as D (electron-donating group)–π (π-conjugated bridge) moiety and the (D–π)2Ph-type fluorescent dye OTK-2 with the two D–π moieties connected through a phenyl ring were derived by oxidative homocoupling of a stannyl D–π unit and Stille coupling of a

• orbital (MO) calculations. Results and Discussion Using a toluene solution containing 1,3-diiodobenzene and (diphenylamino)carbazole-thiophenestannane derivative 1 [33] in the presence of Pd(PPh3)4, the (D–π)2-type and (D–π)2Ph-type fluorescent dyes OTK-2 [33] and OTT-2 were obtained by Stille coupling of

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• polymer 52 in good yields (Scheme 11). The other two polymers 54 and 56 were synthesized through Stille coupling reactions of 46 with 2,6-bis(trimethylstannyl)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b’]dithiophene (53) and tin agent 55, respectively, as shown in the Scheme 12. These polymers 50, 52, 54

Progress in the total synthesis of inthomycins

• Bidyut Kumar Senapati

Beilstein J. Org. Chem. 2021, 17, 58–82, doi:10.3762/bjoc.17.7

• application of various efforts towards the synthesis of inthomycins and their analogues systematically. Keywords: antibiotics; inthomycins; oxazololomycin; Stille coupling; total synthesis; Introduction Inthomycins, alternatively known as phthoxazolins, are a class of compounds in which a methylene

• synthetic efforts toward neooxazolomycin (4), oxazolomycin A (5a), and related antibiotics [17]. The recent review of Lee has mainly focused on the application of copper(I) salt and fluoride-promoted Stille coupling reactions in the synthesis of bioactive molecules including inthomycins A–C (1–3) [18]. The

• Stille coupling between oxazole vinylstannane 24 and dienyl iodide (rac)-20 as the final step. The synthesis began with alcohol (Z)-15a, which was readily prepared in 65% yield from propargyl alcohol (14) by using a copper(I)-catalyzed methyl Grignard addition followed by in situ iodinolysis. The Swern

The biomimetic synthesis of balsaminone A and ellagic acid via oxidative dimerization

• Sharna-kay Daley and
• Nadale Downer-Riley

Beilstein J. Org. Chem. 2020, 16, 2026–2031, doi:10.3762/bjoc.16.169

• Ullman coupling, Suzuki–Miyaura coupling and Stille coupling have dominated the field for the synthesis of biaryls [1][4]. Throughout the years, the exploration of oxidative dimerization reactions of electron-rich aromatic compounds, such as thiophenes, anilines and alkoxyarenes, in an attempt to

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• Pd-catalyzed Stille coupling [26] of 34 with 3-(tributylstannyl)-2-propen-1-ol gave 35. The oxidation of 35 with an excess of MnO2 gave the (2E,4Z)-dienal 36. Alternatively, the Stille coupling of 34 with 3-(tributylstannyl)acrolein also afforded 36. After much experimentation with up to eight amine

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• the protected ᴅ,ʟ-N-Boc-2-bromophenylalanine (89) using a Stille coupling reaction to give the o-vinyl derivative 90 as key intermediate. A hydroboration reaction of compound 90 afforded the primary alcohol 91, which was directly fluorinated and deprotected to give the free amino acids 93 (ᴅ and ʟ

Synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin: experimental and computational evidence for intramolecular and intermolecular C–F···H–C bonds

• Vuyisa Mzozoyana,
• Fanie R. van Heerden and
• Craig Grimmer

Beilstein J. Org. Chem. 2020, 16, 190–199, doi:10.3762/bjoc.16.22

• , numerous methods for the synthesis of these compounds have been developed, examples are the Pechmann condensation [10][11], Stille coupling reaction [12], Knoevenagel condensation [13], Heck coupling reaction [14], Kostanecki reaction, Baylis–Hillman reaction [15], Michael reaction [16], Suzuki–Miyaura

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• ) as alkene component had detrimental effects on the yields in the synthesis of 2d, 2f and 2h. Intermediates 5a and 5b were accessible from 3a and 3b via Suzuki–Miyaura or Stille coupling [34]. Biology The influence on deacetylase activity of three human sirtuin isoforms (Sirt1–3) was determined in a

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D–π–)₂A fluorescent dyes

• Keiichi Imato,
• Toshiaki Enoki,
• Koji Uenaka and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2019, 15, 1712–1721, doi:10.3762/bjoc.15.167

• were prepared by Stille coupling of stannyl compound 1 [3] with 3,5-dibromopyridine, 2,6-diiodopyrazine, and 2,4-dichloro-1,3,5-triazine, respectively (Scheme 1; see Experimental section for the synthetic procedure of OUJ-2). Optical properties The photoabsorption and fluorescence spectra of OUY-2, OUK

• -7000 (Hokuto Denko). Synthesis General synthetic procedure of (D–π–)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 OUY-2 [2], OUK-2 [3] and OUJ-2 were prepared by Stille coupling of stannyl compound 1 [3] with 3,5-dibromopyridine, 2,6-diiodopyrazine, and 2,4-dichloro-1,3,5-triazine, respectively, by using

Stereodivergent approach in the protected glycal synthesis of L-vancosamine, L-saccharosamine, L-daunosamine and L-ristosamine involving a ring-closing metathesis step

• Pierre-Antoine Nocquet,
• Aurélie Macé,
• Frédéric Legros,
• Jacques Lebreton,
• Gilles Dujardin,
• Sylvain Collet,
• Arnaud Martel,
• Bertrand Carboni and
• François Carreaux

Beilstein J. Org. Chem. 2018, 14, 2949–2955, doi:10.3762/bjoc.14.274

• was developed based on a Stille coupling to install the C-linked sugar residue [3]. Moreover, the addition of lithiated glycals to quinone derivatives followed by a rearrangement was also studied for the synthesis of kidamycin according to a “reverse polarity” strategy [4][5]. Considering that the

Fluorescent nucleobase analogues for base–base FRET in nucleic acids: synthesis, photophysics and applications

• Mattias Bood,
• Sangamesh Sarangamath,
• Moa S. Wranne,
• Morten Grøtli and
• L. Marcus Wilhelmsson

Beilstein J. Org. Chem. 2018, 14, 114–129, doi:10.3762/bjoc.14.7

• , however, it lacked a full experimental procedure (Scheme 7). The synthesis started from 6-chloro-7-iodo-7-deazapurine functionalized at the N-9 position with Hoffer’s α-chloro sugar (31, Scheme 7). This material was functionalized further using a Stille coupling to afford a mono-Boc-protected o

• a more straightforward and versatile synthetic route. The Stille coupling was changed to a Suzuki–Miyaura coupling and the cyclization was performed directly starting from the free aniline nitrogen, as we found that Boc protection was required only for cyclization when using DBU and DABCO. To faster

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

Total syntheses of the archazolids: an emerging class of novel anticancer drugs

• Stephan Scheeff and
• Dirk Menche

Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108

• successfully built up. The primary alcohol of fragment 43 was then oxidized by the Dess–Martin reagent (DMP) and then treated with CBr4 and PPh3 to generate the dibromoalkene 44 in high yield of 75% over 2 steps. The group now installed the vinyliodide for the Stille coupling by treating the alkene with

• . Completion of the total synthesis Final assembly of the fragments as shown in Scheme 11 began with an unusual [Ru]-catalyzed Kita esterification due to the instability of fragment 40 towards basic esterification approaches [84]. The following Stille coupling with stannane 39 was then accomplished by CuTC co

• macrocyclic skeleton Based on this unsuccessful approach O‘Neil and co-workers published a new synthetic route towards 2,3-dihydroarchazolid B (3) [48]. As shown in Scheme 13 they were able to synthesize the macrocyclic skeleton 68 by a Stille coupling between stannane 56 and iodide 55 as the key step

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

• Forrest S. Etheridge,
• Roshan J. Fernando,
• Sandra Pejić,
• Matthias Zeller and
• Geneviève Sauvé

Beilstein J. Org. Chem. 2016, 12, 1925–1938, doi:10.3762/bjoc.12.182

• -phenylacetylene analogs afforded the WS3 derivatives in good yield (Scheme 1). We chose to utilize Stille coupling instead of Sonogashira coupling because we had previously found that this method gives higher yields for installing phenylethynyl pyrrolic substituents [9]. The fluorinated tributyltinphenylacetylene

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• regioregular terthiophene and quaterthiophene building blocks were synthesized according to a similar synthetic route starting in high yields. The aldehyde precursors with BDT core CHO-nHT-TBDTs 17–20 were synthesized through a Pd-catalyzed Stille coupling reaction of 9, 11, 13 and 15 with 16, respectively

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications

• Desta Gedefaw,
• Marta Tessarolo,
• Margherita Bolognesi,
• Mario Prosa,
• Renee Kroon,
• Wenliu Zhuang,
• Patrik Henriksson,
• Kim Bini,
• Ergang Wang,
• Michele Muccini,
• Mirko Seri and
• Mats R. Andersson

Beilstein J. Org. Chem. 2016, 12, 1629–1637, doi:10.3762/bjoc.12.160

• National Research Council (CNR) − Institute of Organic Synthesis and Photoreactivity (ISOF), Via P. Gobetti, 101, 40129 Bologna, Italy 10.3762/bjoc.12.160 Abstract Two high bandgap benzodithiophene–benzotriazole-based polymers were synthesized via palladium-catalysed Stille coupling reaction. In order to

Catalytic Chan–Lam coupling using a ‘tube-in-tube’ reactor to deliver molecular oxygen as an oxidant

• Carl J. Mallia,
• Paul M. Burton,
• Alexander M. R. Smith,
• Gary C. Walter and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2016, 12, 1598–1607, doi:10.3762/bjoc.12.156

•  1) over the years with the general goal to overcome the shortcomings of the original Ullman [1] and Goldberg [2] methods relating to the harsh reaction conditions they employ. After a closer look at the work of Mitiga [3] on the Stille coupling reactions, Hartwig [4] and Buchwald [5] independently

Versatile synthesis and biological evaluation of novel 3’-fluorinated purine nucleosides

• Hang Ren,
• Haoyun An,
• Paul J. Hatala,
• William C. Stevens Jr,
• Jingchao Tao and
• Baicheng He

Beilstein J. Org. Chem. 2015, 11, 2509–2520, doi:10.3762/bjoc.11.272

• . Suzuki coupling efficiency in DMF (entries 2 and 3, Table 1) was not as high as Stille coupling (entry 1, Table 1). Suzuki coupling of intermediate 26 with 1-naphthylboronic acid, pyridine-4-boronic acid, pyridine-3-boronic acid and 5-propynylpyridine-3-boronic acid (Method II) (entries 4, 6, 8, and 10

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

• nonsymmetric quaterpyridines; Constable et al. proposed a multistep synthesis of 4’-(alkylthio)quaterpyridines [23] to avoid the Stille palladium-catalyzed coupling, whereas Fallahpour obtained the 4’-nitroquaterpyridine by employing the Stille coupling method [24]. Sauer et al. extended the use of triazine

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• dark purple solid in 95% yield [55]. Polymer 35 is the analogue of the polymer which could have been obtained had the monomer 14a been suitable for electropolymerisation, while Stille coupling of dibromo monomer 14b with 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (36) [78] was used to circumvent

• problems with the electropolymerisation of terthiophene 14c, and to chemically synthesise the analogous polymer 37 [76]. By reacting monomer 14b and 1,2-bis(tributylstannyl)ethylene (38) [79], polymer 39 was synthesised using the Stille coupling protocol [76]. The number average molecular weight (Mn

• monomer compounds 40 and 41, which were synthesised by Stille coupling of diiodopyrrolo-TTF 42 with trimethylstannyl derivatives of EDOT 43 and hexylthiophene 44, were efficiently electropolymerised (Scheme 11) into polymers 45 and 46, respectively [85]. Note that these latter two polymers are analogues

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• was subsequently transformed into a quinolone benzyl ether under reflux conditions. A quinoline triflate ester was prepared from the quinolone and coupled to trimethyl(2-nitrophenyl)stannane by Stille coupling catalyzed by palladium acetate. The afforded nitrophenylquinoline was hydrolyzed and

• , while in method B, the cyclisation was performed in a radical mechanism manner. Whereas the radical condition afforded a low yield of the expected product, the Stille coupling seems to be a better solution. Synthesis of demethyldeoxyamphimedine (9) The synthesis of demethyldeoxyamphimedine was

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• summarized in Scheme 2. The reaction of 6-bromo-2-pyridinecarboxaldehyde or 5-bromo-2-pyridinecarboxaldehyde with one equivalent of TTF-SnMe3 under the Stille coupling conditions, using [Pd(PPh3)4] as catalyst in toluene, afforded the intermediates 6-([2,2’-bi(1,3-dithiolylidene)]-4-yl)picolinaldehyde (1