Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

• synthesize the rotaxane. For example, Anderson and co-workers reported the synthesis of γ-CD–based [2]rotaxane via the Suzuki reaction using a dicarboxylic acid end-capping reagent; they reported a 17% yield (Scheme 1C) [39]. To perform an end-capping reaction in water, multiple hydrophilic substituents

C–C Coupling in sterically demanding porphyrin environments

• Liam Cribbin,
• Brendan Twamley,
• Nicolae Buga,
• John E. O’ Brien,
• Raphael Bühler,
• Roland A. Fischer and
• Mathias O. Senge

Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234

• the Suzuki coupling began with investigating first the Suzuki reaction compatibility of boronic acid 14 with porphyrin 13. Porphyrin 13 and phenylboronic acid (14) were subjected to coupling at 85 °C for 48 hours using Pd2dba3/SPhos as a catalyst/ligand giving porphyrin 26 in a 32% yield, based on a

• dodecasubstituted porphyrins A Miyaura borylation was performed on porphyrin 13, using bis(pinacolato)diboron (B2Pin2), adapting a procedure from the literature [51]. This procedure was further optimized (Table 4) by utilizing conditions in the synthesis of 29 (Table 1, entry 9). Next, a reversed polarity Suzuki

• reaction was performed on the borolanyl porphyrin 46 (Scheme 5). This reaction yielded porphyrin 26 in a 53% yield and tetrapyrenylporphyrin 47 in a 36% yield, respectively. Compared to the synthesis of 26 by Suzuki coupling of para-bromo-phenylporphyrin 13 a significant increase in yield was observed

Negishi-coupling-enabled synthesis of α-heteroaryl-α-amino acid building blocks for DNA-encoded chemical library applications

• Matteo Gasparetto,
• Balázs Fődi and
• Gellért Sipos

Beilstein J. Org. Chem. 2024, 20, 1922–1932, doi:10.3762/bjoc.20.168

• access to compounds featuring C(sp2)–C(sp3) bonds. However, the general view is that this transformation is less reliable than its orthogonal counterpart, the Suzuki reaction. Recent years have seen significant developments in Negishi reaction methodologies [34][35][36][37][38][39]. In particular

Synthesis and properties of 6-alkynyl-5-aryluracils

• Ruben Manuel Figueira de Abreu,
• Till Brockmann,
• Alexander Villinger,
• Peter Ehlers and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 898–911, doi:10.3762/bjoc.20.80

• deactivates the compound for the subsequent Suzuki reaction. Furthermore, lower yields were generally observed when a strong electron-donor or -acceptor was attached to the phenyl group at position 5. Higher yields could be obtained by reducing the steric hindrance at position 5 by introducing a 5-membered

• ), π–π interactions between the alkyne groups can be observed. Moreover, the alkyne phenyl group interacts mainly with molecules between different layers in the vertical direction, while the phenyl group interacts vertically and horizontally with different molecules. The two-fold Suzuki reaction was

• also investigated, but no desired product could be obtained. In fact, starting material 2 appears to be too unreactive to undergo a Suzuki reaction. Reversing the reaction steps gave the desired intermediate 5-bromo-6-phenyl-1,3-dimehtyluracil, which turned out to be unstable. This could be the reason

Mono or double Pd-catalyzed C–H bond functionalization for the annulative π-extension of 1,8-dibromonaphthalene: a one pot access to fluoranthene derivatives

• Nahed Ketata,
• Linhao Liu,
• Ridha Ben Salem and
• Henri Doucet

Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37

• -dibromonaphthalene. Scope of the Pd-catalyzed direct arylation reaction of 2,5-substituted heteroarenes with 1,8-dibromonaphthalene. Scope of the Pd-catalyzed Suzuki reaction followed by direct arylation of arylboronic acids with 1,8-dibromonaphthalene. Attempted reaction of 1-naphthylboronic acid with 1,2

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• Negishi reaction (Zn) [1], Stille reaction (Sn) [2], Kumada reaction (Mg) [3], and Suzuki reaction (Pd) [4] (Scheme 1a). However, these coupling reactions involve a metal exchange step that generates a considerable amount of reaction waste, such as metal salts, which are not environmentally friendly. To

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• electron-donating and electron-withdrawing groups, as well as N-aryl and N-alkylamines (Scheme 15). Lam et al. [58] expanded on the multicomponent method to form substituted dihydropyridobenzazepines 80–82 wherein vinylpyridines 77 are coupled with boronate ester anilines 78 in a Suzuki reaction

An isoxazole strategy for the synthesis of 4-oxo-1,4-dihydropyridine-3-carboxylates

• Timur O. Zanakhov,
• Ekaterina E. Galenko,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2022, 18, 738–745, doi:10.3762/bjoc.18.74

• 11a,c,e–g with NIS/TFA [30]. The reaction of 11d gave the product of double iodination 12c. 4-Iodoisoxazoles 12a,b,d–f were transformed into 3,4-substituted isoxazoles 13a–g by Suzuki reaction using a published procedure with some modifications [31]. Isoxazoles 1, except for isoxazole 1a, were

• )-one 14 in 89% yield. The reaction of pyridone 2e with PBr3 afforded methyl 4-bromo-6-(4-fluorophenyl)-2-phenylnicotinate (15) in 80% yield. The latter was employed in the Suzuki reaction in the high-yield synthesis of 2,4,6-triaryl-substituted nicotinate 16. The nitrogen of 2,3,4,6-tetrasubstituted

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

• one of the key building blocks, 1,3-bisborylated azulene 67 is shown in the Scheme 14. The azulene-DPP polymers containing azulene units connected via 1,3- and 4,7-positions are synthesized in decent yields by using appropriately functionalized azulene and DPP monomers under Suzuki reaction conditions

• -dialkylfluorene-2,7-bis(trimethyleneborate) 102–105 under Suzuki reaction conditions (Scheme 19A). To make the other two polymers, poly{[1,3-bis(9,9’-dihexylfluoren-2’-yl)azulenyl]-alt-[2”,7”-(9”,9”-dialkylfluorenyl]}, 115 and 116, a key azulene-containing building block, 1,3-bis(7-bromo-9,9-dihexylfluoren-2-yl

• -diboronate 103 with varying ratios of 1,3-dibromoazulene (4) and 4,7-dibromoazulene (12) under Suzuki reaction conditions (Scheme 20). As stated above in the case of azulene-thiophene polymers 61–65, the final composition of 1,3- and 4,7-regioisomers of azulene in the polymer chain was determined by 1H NMR

Catalyzed and uncatalyzed procedures for the syntheses of isomeric covalent multi-indolyl hetero non-metallides: an account

• Ranadeep Talukdar

Beilstein J. Org. Chem. 2021, 17, 2102–2122, doi:10.3762/bjoc.17.137

• , 26, and 28. The materials were prepared by the Pd(0)-mediated coupling of lithium N-arylindole-3-alkoxide 21 with 3-bromo-N-arylindole 22, followed by a further C-2 bromination (24) and subsequent Suzuki reaction with boronic acids 27 or 25 (Scheme 4) [42]. A similar class of molecules have found

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• derivatives is based on the Suzuki reaction. At the same time, pyrene-1-ylboronic acid and 6,6'-dibromoisoindigo were used to introduce a pyrene fragment directly into the isoindigo nucleus, and to obtain a thiophene analogue, pyrenyl-substituted 2-bromothiophene and 6,6'-bis(4,4,5,5-tetramethyl-1,3,2

• [36] do not give the exact values of the molecular weight of the obtained polymers, they draw a conclusion about the influence of the molecular weight on the efficiency of the cells (Table 4). Thus, when using polymer 24b obtained by the Suzuki reaction with bis(pinacolato)diboron, the OSC efficiency

Cascade intramolecular Prins/Friedel–Crafts cyclization for the synthesis of 4-aryltetralin-2-ols and 5-aryltetrahydro-5H-benzo[7]annulen-7-ols

• Jie Zheng,
• Shuyu Meng and
• Quanrui Wang

Beilstein J. Org. Chem. 2021, 17, 1481–1489, doi:10.3762/bjoc.17.104

• subjected to a Suzuki reaction with pinacol vinylboronate using Pd(dppf)Cl2 as catalyst to produce 3-(2-vinylphenyl)propan-1-ol (18). The oxidation of alcohol 18 with Dess–Martin oxidizing reagent furnished the requisite aldehyde 19 in 43% yield over the three steps. Under the standard conditions, aldehyde

Synthesis of 4-substituted azopyridine-functionalized Ni(II)-porphyrins as molecular spin switches

• Jannis Ludwig,
• Tobias Moje,
• Fynn Röhricht and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2589–2597, doi:10.3762/bjoc.16.210

• -iodophenylazo)-4-chloropyridine (17) with LiSSiMe3 (8) [28], t-BuSH (13) and HSCH2CH2CO2CH3 (15) [29]. Electron-deficient aromatic, silylated thiols exhibit very labile Si–S bonds [30]. Thus, even bulky silyl protection groups are not suitable as protecting groups for the subsequent Suzuki reaction

• described by Sato et al. [31] of 20 yielded 3-(3-bromophenylazo)-4-pyridinecarboxylic acid (21, Scheme 3). Synthesis of the Ni(II)-porphyrins The phenylboronic acid pinacol ester 22 was used as a component for the Suzuki reaction (Scheme 4). No conversion was observed for the Suzuki reaction of the

• porphyrin 22 and the disulfide 12, obviously because of catalyst poisoning by sulfur [32][33]. To circumvent these problems, protection groups were introduced. Protection with methyl 3-mercaptopropionate (15) [29] was successful, however, inhibition of the Suzuki reaction was observed. We assume an alkaline

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• 95d was assembled through Suzuki reaction of hexabromosumanene with 4-pyridylboronic acid as detailed in the above section. Having the hexapyridylsumanene 95d in hand, it was dissolved in MeOH/CHCl3 solution and then the MeOH solution of Zn(NO3)2·6H2O was diffused into it for several days to afford

Azo-dimethylaminopyridine-functionalized Ni(II)-porphyrin as a photoswitchable nucleophilic catalyst

• Jannis Ludwig,
• Julian Helberg,
• Hendrik Zipse and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2119–2126, doi:10.3762/bjoc.16.179

• -1, blue), and 1 at PSS530nm (predominantly cis-1, green). The background reaction was determined with porphyrin 8 (cyan dots) and for a sample without catalyst or reference compounds (red stars). Synthesis of 4-N,N-dimethylamino record player molecule 1 by Suzuki reaction between Ni-porphyrin

Suzuki–Miyaura cross coupling is not an informative reaction to demonstrate the performance of new solvents

• James Sherwood

Beilstein J. Org. Chem. 2020, 16, 1001–1005, doi:10.3762/bjoc.16.89

• coupling is often unaffected by the choice of solvent, and therefore the Suzuki–Miyaura reaction provides limited information regarding the usefulness of any particular solvent for organic synthesis. Keywords: cross coupling; green solvents; palladium; solvent selection; Suzuki reaction; Findings The

Design and synthesis of diazine-based panobinostat analogues for HDAC8 inhibition

• Sivaraman Balasubramaniam,
• Sajith Vijayan,
• Liam V. Goldman,
• Xavier A. May,
• Kyra Dodson,
• Sweta Adhikari,
• Fatima Rivas,
• Davita L. Watkins and
• Shana V. Stoddard

Beilstein J. Org. Chem. 2020, 16, 628–637, doi:10.3762/bjoc.16.59

• literature procedure [39]. The intermediate 21 was then subjected to the Suzuki reaction using conditions already developed to provide the ester aldehyde 17 in overall yield of 16% for two steps. Having identified synthetically suitable conditions for compound 17, we scaled up the reaction to complete the

A chemically contiguous hapten approach for a heroin–fentanyl vaccine

• Yoshihiro Natori,
• Candy S. Hwang,
• Lucy Lin,
• Lauren C. Smith,
• Bin Zhou and
• Kim D. Janda

Beilstein J. Org. Chem. 2019, 15, 1020–1031, doi:10.3762/bjoc.15.100

• obtain an aldehyde that could then be used in a reductive amination. Beginning with the commercially available 4-(4-bromophenyl)butanoic acid, an alkene was installed with a Suzuki reaction, which in turn underwent ozonolysis to give 21, shown in Scheme 4. In parallel, a commercially available piperidine

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• ]. Mechanochemical Suzuki reaction [56]. Mechanochemical Suzuki–Miyaura coupling by LAG [57]. Mechanochemical Heck reaction [59]. a) Sonogashira coupling under milling conditions. b) The representative example of a double Sonogashira reaction of p-iodoacetophenone with 1,4-bis-ethynyl benzene. Copper-catalyzed CDC

Encaging palladium(0) in layered double hydroxide: A sustainable catalyst for solvent-free and ligand-free Heck reaction in a ball mill

• Wei Shi,
• Jingbo Yu,
• Zhijiang Jiang,
• Qiaoling Shao and
• Weike Su

Beilstein J. Org. Chem. 2017, 13, 1661–1668, doi:10.3762/bjoc.13.160

• -assisted method to prepare Pd catalysts immobilized on modified chitosan (Scheme 1). Although these catalysts were found to be effective in the Suzuki reaction after three cycles, the modification conditions of chitosan were rigorous. As catalyst-supported material, layered double hydroxides (LDHs) have

Total synthesis of elansolids B1 and B2

• Liang-Liang Wang and
• Andreas Kirschning

Beilstein J. Org. Chem. 2017, 13, 1280–1287, doi:10.3762/bjoc.13.124

• an optimized C–C cross-coupling sequence with a Suzuki cross-coupling reaction as key step. Keywords: antibiotics; polyenes; polyketides; Stille reaction; Suzuki reaction; total synthesis; Introduction The elansolids are metabolites from the gliding bacterium Chitinophaga sancti (formerly

Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines

• David R. Chisholm,
• Garr-Layy Zhou,
• Ehmke Pohl,
• Roy Valentine and
• Andrew Whiting

Beilstein J. Org. Chem. 2016, 12, 1851–1862, doi:10.3762/bjoc.12.174

• addition of DIBAL to 20a.a DIBAL reductions of quinolin-2-ones 23a–e using the optimised method to synthesise 22.a Comparing the reactivity of 6-iodo-THQ 21 and 6-bromo-THQ 26 in a typical Suzuki reaction with boronic ester 27 to give biaryl 28. Supporting Information Supporting information features full

Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1170–1177, doi:10.3762/bjoc.12.112

• the accidental chlorination of the picolinic acid precursor (Scheme 2) – offered the option to perform two subsequent coupling reactions in a controlled fashion. In the first step, the more reactive nonaflate moiety of 5g was efficiently substituted by a phenyl group under standard Suzuki reaction

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

• and Suzuki reaction conditions. To this end, 2-(tributylstannyl)furan was coupled with 6-chloropurine nucleoside 26 by Stille cross coupling [47][48] catalyzed by bis(triphenylphosphine)palladium(II) chloride in DMF (Method I) (Scheme 3). The resulting 6-aryl compound 30 was obtained in 91% yield and

• -chlorine atom on the intermediate 42 was stable under the Stille and Suzuki reaction conditions and under ammonia deprotection conditions. However, the palladium-catalyzed cross coupling of dichloro-intermediate 42 with organostannane and organoboronic acid reagents resulted in lower yields when compared

• Stille and Suzuki cross-coupling reactions. 3’-Deoxy-3’-fluororibofuranosyl 2-chloropurine nucleosides 17–20 were synthesized by the similar strategy from the key intermediate 42. DME–water was found to be an efficient solvent system for Suzuki reaction on challenging substrates. De-chlorination of the 6

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