Palladium-catalyzed benzocyclization reactions of quinoline-2-carboxamides via sequential C–H/N–H functionalization

• Shoichi Sugita,
• Kentaro Okano and
• Atsunori Mori

Beilstein J. Org. Chem. 2026, 22, 905–914, doi:10.3762/bjoc.22.71

• carbon–heteroatom bonds. The classical coupling reactions, such as Kumada–Tamao–Corriu coupling [11][12][13], Sonogashira coupling [14][15], Negishi coupling [16][17], Migita–Kosugi–Stille coupling [18][19][20], Suzuki–Miyaura coupling [21][22], and Hiyama coupling [23][24] involve carbon–halogen and

Get a better glimpse on sequential photoreactions of trisnorbornadienes with ¹⁹F NMR spectroscopy

• Julian Felix Maria Hebborn,
• Ben Eric Merten,
• Thomas Paululat and
• Heiko Ihmels

Beilstein J. Org. Chem. 2026, 22, 527–534, doi:10.3762/bjoc.22.38

• storage. The target compound was readily synthesized by a Suzuki–Miyaura coupling reaction and examined with respect to the key properties for MOST applications. Upon direct or photosensitized irradiation, the trisnorbornadiene was transformed stepwise and almost quantitatively into the corresponding

• trisnorbornadiene 1f was synthesized in 36% yield through a Suzuki–Miyaura coupling reaction of tribromotrifluorobenzene 3 with the 2-borononorbornadiene 1e (Scheme 2) [43]. The product 1f was identified and fully characterized by NMR spectroscopy (1H, 13C, 19F, COSY, HSQC, HMBC), mass spectrometry, melting point

• comparison of the synthesis and photophysical properties of the fluoro-substituted norbornadiene 1f with the ones of the parent compound 1b revealed that the yield of the Suzuki–Miyaura coupling reaction is significantly lower for the former [22], presumably because of the steric hindrance induced by the

Recent advances in the stereoselective synthesis of distal biaxially chiral molecules

• Fanxing Zhou,
• Chen Zhang,
• Lingyu Sun,
• Yiyun Fang,
• Siming Zheng,
• Lina Hu,
• Mengyang Shen,
• Zhen Zhao,
• Wei Xu,
• Yunqiang Sun and
• Zi-Qiang Rong

Beilstein J. Org. Chem. 2026, 22, 461–479, doi:10.3762/bjoc.22.34

• -dibromonaphthalenes (45). Notably, the reaction achieved the synthesis of ternaphthalenes with excellent optical purity exceeding 95% ee. In 2014, Tang and co-workers pioneered the first asymmetric synthesis of functionalized chiral biaryl natural products with high enantioselectivity via Suzuki–Miyaura coupling

• -workers [35]. Synthesis of chiral homoaryl compounds by Suzuki–Miyaura coupling. Structurally complex APIs with multiple chiral axes. Synthesis of helicenes containing stereogenic axes. Chiral NHC–Pd complex-catalyzed Suzuki–Miyaura cross-coupling reaction for the synthesis of block-transfer isomeric

Measuring the stereogenic remoteness in non-central chirality: a stereocontrol connectivity index for asymmetric reactions

• Ivan Keng Wee On,
• Yu Kun Choo,
• Sambhav Baid and
• Ye Zhu

Beilstein J. Org. Chem. 2025, 21, 1995–2006, doi:10.3762/bjoc.21.155

• –B [14] (Scheme 3E) bonds. In the case of an asymmetric cross-coupling reaction (Scheme 3C) [10], both sets of the substituents on individual aryl groups are considered because neither is involved in the bond formation/cleavage. Accordingly, the catalyst-controlled atroposelective Suzuki–Miyaura

• coupling of biaryls is designated as [30 20]. In addition to biaryls, axially chiral allenes are popular targets for asymmetric synthesis. Three examples of asymmetric reactions that form axially chiral allenes are shown in Scheme 4. For example, the enantioselective nucleophilic substitution to yield

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• with 99% ee. The TBS protection was crucial to prevent the potential racemization by intramolecular transesterification. Ester 79 was then prepared from 78 in eight steps. To complete the dimerization, fragments 80 and 81 were independently prepared from 79. An intermolecular Suzuki–Miyaura coupling

Photoswitches beyond azobenzene: a beginner’s guide

• Michela Marcon,
• Christoph Haag and
• Burkhard König

Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143

Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning

• Pablo Quijano Velasco,
• Kedar Hippalgaonkar and
• Balamurugan Ramalingam

Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3

• selection, a dispensing module for solids and liquids, a reaction module capable of heating and stirring, a sample preparation module, and a LC–MS characterization module (Figure 2d). The efficiency of the system has been demonstrated in three reactions types, namely Suzuki–Miyaura coupling, Buchwald

• drug molecules autonomously, and it does not include a closed-loop optimization framework. The Pfizer research team developed a custom-designed flow system for rapid reaction screening of the Suzuki–Miyaura coupling reaction on a nanomolar scale [50]. The platform included a modified HPLC system that

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• boronic esters of 1,8-DHN have recently been investigated and reported by Krempner and co-workers [51]. To our delight, the Suzuki–Miyaura coupling/intramolecular C–H arylation sequence between 12 and boronic ester 17d proceeded smoothly affording product 15a in 84% yield. The results summarized in Table

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

• porphyrin architectures, which could be used in supramolecular assemblies, catalysis, or sensing. In this work a library of arm-extended dodecasubstituted porphyrins was synthesized through the optimization of the classic Suzuki–Miyaura coupling of peripheral haloaryl substituents with a range of boronic

• -workers for the synthesis of meso-substituted aryl bis-pocket porphyrins [34]. Therein catalysts Pd(dppf)Cl2 and Pd(PPh3)3 were identified to be the most effective for accomplishing the Suzuki–Miyaura coupling at the ortho-position of the meso-phenyl position in sterically hindered planar porphyrins

• . Conclusion When considering sterically demanding systems with haloaryl and boronic acids as substrates for the Suzuki–Miyaura coupling, many may consider 2,6-alkyl-disubstituted phenyl rings as a model sterically demanding system to test the robust nature of both metal catalyst and ligand, for example, much

Machine learning-guided strategies for reaction conditions design and optimization

• Lung-Yi Chen and
• Yi-Pei Li

Beilstein J. Org. Chem. 2024, 20, 2476–2492, doi:10.3762/bjoc.20.212

• simply memorize the most frequently reported solvents and reagents in the literature. Beker et al. [178] showed that some machine learning models could not outperform simple statistical analyses based on the popularity of reported conditions in the literature, using the Suzuki–Miyaura coupling as an

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• Suzuki–Miyaura coupling with boronic ester 53 and O-acetylation furnished 54. The dienophile component, morachalcone A (44), was synthesized from phenol 55 in four steps including O-prenylation and subsequent Claisen rearrangement, aldol condensation with 56, and deprotection. The key chemo-enzymatic

Introduction of peripheral nitrogen atoms to cyclo-meta-phenylenes

• Koki Ikemoto and
• Hiroyuki Isobe

Beilstein J. Org. Chem. 2024, 20, 1207–1212, doi:10.3762/bjoc.20.103

• achieved with one-pot Suzuki–Miyaura coupling to arrange phenylene rings and pyridinylene rings in an alternating fashion. Analyses with UV–vis spectroscopy showed changes in the photophysical properties with nitrogen doping, and X-ray crystallographic analyses experimentally revealed the presence of

• were installed in an outward-radiated manner, which expands the structural diversity to exploit the chemistry at the periphery of [n]CMP (Figure 1b). Through the use of Suzuki–Miyaura coupling for macrocyclisation, pyridinyl and phenylene rings were assembled in an alternating fashion, which afforded

• -doped [n]CMPs, 3a and 3b, were synthesized via one-pot Suzuki–Miyaura coupling [12] (Scheme 1). Previously, we synthesized [n]CMPs with inward-focused nitrogen dopants by using Suzuki–Miyaura coupling with Pd(PPh3)4 as the catalyst [13] and applied this method to outward-radiated congeners in this work

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• carbon monoxide insertion, and Suzuki–Miyaura coupling reaction, from 2-gem-dibromovinylaniline [12]. In the presence of Pd(PPh3)4 (5 mol %) as catalyst, 5 equivalents of base (K2CO3), an aryl- or heteroarylboronic ester (1.1 equivalents), CO (12 bar), in dioxane at 100 °C after 16 h the indole

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• phenanthrene as the main product. This result highlights the higher sensitivity of the Te-heteropines compared to S- and Se-counterparts towards thermal chalcogen extrusion. Next, four-fold Suzuki–Miyaura coupling of the tetrabrominated tribenzoheteropines 25b and 25c delivered compounds 27b and 27c as direct

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

• –cyclization of common synthetic intermediates 94 and 95 (Scheme 8). Compound 94 was obtained in three steps, with the key step being the Suzuki–Miyaura coupling of appropriately functionalized precursors 91 and 92 using Romo and co-worker’s protocol [52]. Reaction of 94 under PPTS acidic conditions initiated

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• chromatography, in a manner similar to a reported procedure [49]. In a manner similar to [40], intermediate 27 was reacted with 32 within a Suzuki–Miyaura coupling to achieve 33 (Scheme 4). Intermediate 33 was then hydrolysed to the diacid 34 with lithium hydroxide [15]. Compound 34 was successfully reacted

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry

• Koji Kubota,
• Emiru Baba,
• Tamae Seo,
• Tatsuo Ishiyama and
• Hajime Ito

Beilstein J. Org. Chem. 2022, 18, 855–862, doi:10.3762/bjoc.18.86

• organic materials, typically through Suzuki–Miyaura coupling [1][2][3][4][5][6][7]. The palladium-catalyzed boryl substitution of aryl halides with boron reagents, termed Miyaura–Ishiyama borylation, is an efficient method for synthesizing arylboronates with high functional group compatibility [8][9][10

Borylated norbornadiene derivatives: Synthesis and application in Pd-catalyzed Suzuki–Miyaura coupling reactions

• Robin Schulte and
• Heiko Ihmels

Beilstein J. Org. Chem. 2022, 18, 368–373, doi:10.3762/bjoc.18.41

• -dioxaborolane was prepared and shown to be a suitable substrate for Pd-catalyzed Suzuki–Miyaura coupling reactions with selected haloarenes. It was demonstrated exemplarily that the novel monosubstituted 2-(1-naphthyl)norbornadiene, that is accessible through this route, is transformed to the corresponding

• derivatives may be metalated in a Li–halogen exchange reaction [27]. In another versatile approach, arylation and alkenylation reactions of the norbornadiene may be accomplished with a Suzuki–Miyaura coupling reaction. In this case, halogenated norbornadienes react with arylboronic acids or their esters to

• the corresponding aryl-substituted norbornadienes under optimized conditions [28][29][30][31]. To the best of our knowledge, however, no borylated norbornadiene derivatives have been employed in Suzuki–Miyaura coupling reactions so far, although this synthetic route appears to be a useful

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

• Tomáš Chvojka,
• Athanasios Markos,
• Svatava Voltrová,
• Radek Pohl and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 2657–2662, doi:10.3762/bjoc.17.179

• -diaryl-substituted enamides is observed. Thus, the method provides synthetic access to both isomers of the target enamides from (Z)-β-enamido triflates. Keywords: enamides; isomerization; Suzuki–Miyaura coupling; vinyl triflates; Introduction Enamides are substrates of high value in organic synthesis

Silica gel and microwave-promoted synthesis of dihydropyrrolizines and tetrahydroindolizines from enaminones

• Robin Klintworth,
• Garreth L. Morgans,
• Stefania M. Scalzullo,
• Charles B. de Koning,
• Willem A. L. van Otterlo and
• Joseph P. Michael

Beilstein J. Org. Chem. 2021, 17, 2543–2552, doi:10.3762/bjoc.17.170

• the unsubstituted pyrrole position (Scheme 5). This site was readily brominated with N-bromosuccinimide in N,N-dimethylformamide [71] to afford ethyl 7-bromo-6-phenyl-2,3-dihydro-1H-pyrrolizine-5-carboxylate (28) in 83% yield. Palladium(0)-catalyzed Suzuki–Miyaura coupling of 28 with phenylboronic

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• to 91% yield. The trifold Suzuki–Miyaura coupling product, i.e., 2,4,9-triphenyl-5,6,7,8-tetrahydroacridine, could not be prepared, even after increasing the amount of phenylboronic acid to 4 equivalents and prolonging the reaction time. Our primary screening consisted in evaluating the effect of the

• ) approach [71] at the restricted Becke, 3-parameter, Lee–Yang–Parr hybrid functional (B3LYP) with standard basis set 6-31G (d) were carried out. Experimental procedure for the Suzuki–Miyaura coupling and spectroscopic data for 9-chloro-2,4-diaryl-5,6,7,8-tetrahydroacridine derivatives 4a–g 2,4-Dibromo-9

• at a scan rate of 50 mV/s. Synthesis of 2. Synthesis of compounds 4a–g. Optimization of the Suzuki–Miyaura coupling between 2 and 3a.a Photophysical properties of tetrahydroacridines 4a–d in dichloromethane solution. Selected bonding and non-bonding distances (Ǻ) for compounds 4a–d. Supporting

Synthesis of phenanthridines via a novel photochemically-mediated cyclization and application to the synthesis of triphaeridine

• Songeziwe Ntsimango,
• Kennedy J. Ngwira,
• Moira L. Bode and
• Charles B. de Koning

Beilstein J. Org. Chem. 2021, 17, 2340–2347, doi:10.3762/bjoc.17.152

• was demonstrated to be useful for the synthesis of the natural product trisphaeridine (3) [17]. Exposure of 1-bromo-2,4,5-trimethoxybenzene (19) to Suzuki–Miyaura coupling reaction conditions with boronic acid 20 resulted in the formation of aldehyde 21 (Scheme 5). Treatment of 21 with hydroxylamine

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

• synthesized from tropolone (21) in five steps (Scheme 21A). The Suzuki–Miyaura coupling reaction of 2,6-dibromoazulene (125) with 2,2’-(9,9-dioctyl-9H-flourene-2,7-diyl)di(1,3,2-dioxaborolane) (103) furnished the polymer 126 in 31% yield (Scheme 21B). The other polymer 129 was obtained from 2,6-dibromoazulene

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• ). Representative examples included indenoanthracenes 61a–c, bearing aryl groups linked to the alkyne, and indenoanthracenes 61d–f, containing tetramethylsilane groups at the terminal alkyne [46]. From commercially available 1,8-dichloroanthraquinone (62) and by using modified Suzuki–Miyaura coupling reaction

• conditions, Agarwal et al. synthesized a series of 1,8-diarylanthracene derivatives 64 in two steps (Scheme 14) [47]. First, the simple reduction of anthraquinone 62 employing the well-known reductive Zn/NH3 system and HCl provided 1,8-dichloroanthracene (63). A Suzuki–Miyaura coupling reaction in the

• -bromonaphthoquinone (140) reacted with vinylacetic acid to afford the allylated compound 141. Then, reduction of 141 and sequential O-methyl-protection furnished naphthalene 142. A Suzuki–Miyaura coupling reaction between 142 and boronic acids afforded 2-naphthylbenzaldehydes 143, which were further subjected to a

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

• catalysts in various organic reactions [1] such as the Ullmann coupling, Suzuki coupling, Suzuki–Miyaura coupling, and the Heck reaction. Aside from being useful synthetic agents, biguanides gained particular interest from the perspective of medicinal chemistry. For the first time, the biological activity