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

3,3'-Linked BINOL macrocycles: optimized synthesis of crown ethers featuring one or two BINOL units

• Somayyeh Kheirjou,
• Jan Riebe,
• Maike Thiele,
• Christoph Wölper and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2025, 21, 1719–1729, doi:10.3762/bjoc.21.134

• ]. For the synthesis of macrocycles M2 with two BINOL units, we relied on the monoiodide 12, which was first reacted in a two-fold Suzuki coupling to install the first linker, followed by silyl deprotection and introduction of the second linker via nucleophilic substitution [51]. Both procedures require

• synthetic approaches (see Figure 1e) toward BINOL macrocycles had successfully used either Williamson-type reactions or Suzuki couplings for the synthesis of intermediates. Thus, we chose to compare the use of two-fold Suzuki coupling or two-fold Williamson reaction for the synthesis of macrocycles M1. For

• the approach via Suzuki coupling, we employed the previously reported BINOL-diiodide 1 [52], which was reacted with bisboronic acids (see Figure 3a). Here we chose bisboronic esters 75/6/7/8 which feature dimethylphenyl groups that are linked via penta/hexa/hepta/octaethylene glycol chains (throughout

Synthesis of an aza[5]helicene-incorporated macrocyclic heteroarene via oxidation of an o-phenylene-pyrrole-thiophene icosamer

• Yusuke Matsuo,
• Aoi Nakagawa,
• Shu Seki and
• Takayuki Tanaka

Beilstein J. Org. Chem. 2025, 21, 1561–1567, doi:10.3762/bjoc.21.119

• hybrid decamer 3 in a previous report [26], via a Suzuki–Miyaura cross-coupling reaction between dibromo precursor 1 and borylated precursor 2 (Scheme 1). The resulting mixture was successfully separated by column chromatography on silica using CH2Cl2/n-hexane as an eluent to give icosamer 4 in 6% yield

• common organic solvents. Conclusion A novel o-phenylene-pyrrole-thiophene hybrid macrocycle (icosamer 4) was synthesized via Suzuki–Miyaura cross-coupling and isolated in 6% yield. Oxidation of 4 with PIFA produced a partially fused aza[5]helicene-containing macrocycle 5 in 58% yield, which was also

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• , Howell et al. recently disclosed a general method for the synthesis of 2-halomethylideneoxetanes through halogenation of 2-methylideneoxetanes using N-halosuccinimides, and illustrated their synthetic utility by Suzuki–Miyaura, Sonogashira and Buchwald–Hartwig coupling reactions [53]. In addition to Cu

• high yields. Further transformations were also investigated such as a Suzuki coupling (at the aryl group) or oxidation to sulphoxides and sulphones, demonstrating the versatility of these products. In addition, their medicinally relevant physicochemical properties such as lipophilicity, clearance and

• Suzuki coupling to tether the oxetane with the nucleophile, and gave moderate to high yields (Scheme 48b). The last one employed an Ullman or Buchwald–Hartwig coupling and provided access to various benzomorpholines 203 with good functional group tolerance (Scheme 48c). In 2020, Sun et al. reported a

Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes

• Bartłomiej Pigulski

Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99

• cross-coupling reactions, such as the Suzuki sp2–sp2 coupling or Sonogashira sp2–sp coupling. These reactions enable the modular construction of complex precursors, which can then be transformed into azulene-embedded PAHs in the final step. Two main synthetic strategies are commonly employed: 1) The

• exceptionally high yield (97%). A Suzuki cross-coupling reaction between 47 and 45 gave compound 48 which was subjected to a final Scholl oxidation using DDQ. The target compound 49, containing two azulene subunits, was obtained in a relatively low yield (16%). Analysis of NICS values for 49 revealed similar

• can also serve as valuable synthetic tools for constructing azulene subunits in the final step. For example, Ma and co-workers reported a modular synthetic strategy for the synthesis of diverse azulene-embedded PAHs via a tandem Suzuki coupling and base-promoted Knoevenagel-type condensation

A versatile route towards 6-arylpipecolic acids

• Erich Gebel,
• Cornelia Göcke,
• Carolin Gruner and
• Norbert Sewald

Beilstein J. Org. Chem. 2025, 21, 1104–1115, doi:10.3762/bjoc.21.88

• accordance with coupling constants and resulting dihedral angles. Keywords: conformational restraints; dihedral angle NMR; half-chair conformation; modified amino acids; pipecolic acid; stereoselective hydrogenation; Suzuki–Miyaura cross-coupling; Introduction Non-proteinogenic amino acids play an

• structure of pipecolic acid is rather challenging and often necessitates early-stage derivatization followed by the formation of the six-membered ring [29][30][31][32]. An alternative is to utilise derivatization reactions such as Suzuki–Miyaura [33] or Sonogashira–Hagihara [34] cross-coupling reactions on

• a key intermediate product. This late-stage approach was previously described by us while utilising Suzuki–Miyaura or Sonogashira–Hagihara cross-coupling reactions to generate pipecolic acid derivatives with alkynyl substituents in the C6 position [35]. Here, we present a robust synthetic route to

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

Studies on the syntheses of β-carboline alkaloids brevicarine and brevicolline

• Benedek Batizi,
• Patrik Pollák,
• András Dancsó,
• Péter Keglevich,
• Gyula Simig,
• Balázs Volk and
• Mátyás Milen

Beilstein J. Org. Chem. 2025, 21, 955–963, doi:10.3762/bjoc.21.79

• brevicarine (2) could not be detected by LC–MS. As regards our plans for an alternative synthesis of racemic brevicolline ((±)-1), our primary goal was the direct coupling of the pyrrole ring to compound 3, instead of its ring-closing construction shown in Scheme 1. Suzuki reaction of 3 with pyrrole boronic

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• different substituents and polysubstituted annular boronic acids 98, a Suzuki coupling was employed to synthesize advanced isoquinoline intermediates 100. Following this, a 6π electrocyclization reaction and nucleophilic reaction were developed to achieve C–C and C–N bond constructions, respectively

Synthesis and photoinduced switching properties of C₇-heteroatom containing push–pull norbornadiene derivatives

• Daniel Krappmann and
• Andreas Hirsch

Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64

• a subsequent Suzuki cross-coupling reaction with (4-(diphenylamino)phenyl)boronic acid was performed. The reaction conditions were adapted from prior experiments with C-NBD1 [40] and further refined for the heterocyclic analogues. Optimal results were achieved using K2CO3, Pd(OAc)2 and RuPhos with

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• -dechlorination product was observed. This notable result suggests performing a second coupling using conventional chemical methods, such as the Suzuki–Miyaura reaction. Furthermore, the coupling yield decreased for phenyl bromides bearing bulky ortho-substituents while hydrodehalogenation byproducts formed. The

Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra

• Yuuki Ishii,
• Minoru Yamaji,
• Fumito Tani,
• Kenta Goto,
• Yoshihiro Kubozono and
• Hideki Okamoto

Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53

• Suzuki (Okayama University) for solid-state absorption spectral measurements. Funding The present study was supported by Grants-in-Aid for Scientific Research, KAKENHI, from JSPS, Japan (JP18H02043, JP20K05648, JP23K04877), and by the Cooperative Research Program of the ‘Network Joint Research Centre for

Synthesis of the aggregation pheromone of Tribolium castaneum

• Biyu An,
• Xueyang Wang,
• Ao Jiao,
• Qinghua Bian and
• Jiangchun Zhong

Beilstein J. Org. Chem. 2025, 21, 510–514, doi:10.3762/bjoc.21.38

• male, is attractive to both sexes [12]. Later, Suzuki identified the compound as 4,8-dimethyldecanal [13]. Mori synthesized four possible stereoisomers of 4,8-dimethyldecanal, and found that the response of T. castaneum to the (4R,8R)-isomer was identical to the natural pheromone [14][15]. In 2011

Synthesis of N-acetyl diazocine derivatives via cross-coupling reaction

• Thomas Brandt,
• Pascal Lentes,
• Jeremy Rudtke,
• Michael Hösgen,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2025, 21, 490–499, doi:10.3762/bjoc.21.36

• -substituted diazocines were prepared via Stille, Suzuki, and Buchwald–Hartwig reactions. X-ray structures are presented for derivatives 1, 2 and 7. Keywords: cross-coupling; diazocine; N-acetyl diazocine; photoisomerization; photoswitch; thermal relaxation; Introduction Diazocines are frequently used

• of 74% for bromine 2 and 78% for iodo starting material 3 (Table 3) [24]. To overcome the problems of poor yields in the arylation of N-acetyl diazocines via Stille coupling we used Suzuki–Miyaura reactions of the diazocines 2 and 3 with different arylboronic acids [25][26]. There are several

• examples of last-step modifications of azobenzenes via Suzuki–Miyaura reactions in the current literature, which indicate that the reaction conditions are compatible with azo groups [27][28]. Suzuki–Miyaura reaction of 2 and 3 with different phenylboronic acids resulted in the formation of the

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• . Also in this case, the addition of toluene was beneficial and excellent yield of the corresponding product (10.2) was observed in 30 h of reaction. As a comparison, the latter reaction required 48 h in solution. Intriguingly, 10.3 could in turn be synthesized via a mechanochemical Suzuki coupling

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

• of stereoselective Suzuki–Miyaura couplings, offering precise control over both categorical and continuous variables (Figure 2a) [15]. The integrated robotic system containing a four-needle dispense head facilitated the delivery of reagents in low volume and slurries, ensuring the accuracy and

• Buchwald–Hartwig aminations [16][17][18][19], Suzuki couplings [16][17][20], N-alkylations [21], hydroxylations [22], and photochemical reactions [23][24][25][26][27][28][29]. The versatility to handle multiple reagents and the widespread availability of 96-well plates have facilitated the extensive

• 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

Synthesis, structure and π-expansion of tris(4,5-dehydro-2,3:6,7-dibenzotropone)

• Yongming Xiong,
• Xue Lin Ma,
• Shilong Su and
• Qian Miao

Beilstein J. Org. Chem. 2025, 21, 1–7, doi:10.3762/bjoc.21.1

•  1) featuring three heptagons and two pentagons, with its structure confirmed by X-ray crystallography. This π-expansion approach of compound 1 differs from the method reported by Müllen and co-workers, which involves Ramirez olefination and Suzuki coupling, resulting in the expansion of a seven

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

• %). This cascade involves an initial Suzuki–Miyaura cross-coupling reaction between 1,8-dihalonaphthalenes and heteroarylboronic acids or esters, followed by an intramolecular C–H arylation under the same conditions to yield the final heterocyclic fluoranthene analogues. The method was further employed to

• )-catalyzed [2 + 2 + 2] cycloaddition reactions with 1,8-dialkynylnaphthalenes to access azafluoranthenes and 2-pyridone-fused naphthalenes [27]. In 2017, we reported a Pd-catalyzed cascade reaction that involves a sequential Suzuki–Miyaura cross-coupling and a subsequent intramolecular C–H arylation between

• 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

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• ) was synthesized via consecutive Suzuki coupling and Scholl reaction in a total yield of 77%. The synthesis, molecular structures, nomenclature, and synthetic yields of all compounds are shown in general Scheme 1. All prepared molecules were fully characterized by NMR (1H, 19F and 13C), HRMS, and CHN

• '-tetraalkoxy-1,1'-biphenyl (2Br-BPn → 2Li-BPn) e.g., 4F-TPn [44], p-TPFn [46], m-TPFn [46], PHn [45], and Fn (this work); BTPn was synthesized by a Suzuki–Scholl reaction sequence (Scheme S3, Supporting Information File 1). Single crystal structure of 1,2,4-trifluoro-3-(perfluorophenyl)triphenylene (F) viewed

Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling

• John M. Halford-McGuff,
• Thomas M. Richardson,
• Aidan P. McKay,
• Frederik Peschke,
• Glenn A. Burley and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2024, 20, 3198–3204, doi:10.3762/bjoc.20.265

• to chemical biology (Scheme 3a). The utility of the germanyl triazole products was then assessed by subsequent derivatisation of exemplar compounds 15 and 21 (Scheme 3b). Chemoselective Suzuki–Miyaura cross-coupling of the BPin moiety in 21 was straightforward, giving 28 in excellent yield [73

• ]. Similarly, cross-coupling of the GeEt3 moiety in 15 under conditions developed by Schoenebeck and co-workers gave 29 [57]. Bromodegermanylation using NBS employing conditions from Schoenebeck gave bromotriazoles 30 and 31 in moderate to excellent yield [62]. These could then undergo Suzuki–Miyaura cross

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

• substitution/addition reactions became the standard for end-capping reactions, although a transition metal–catalyzed cross-coupling reaction has also been used to synthesize CD-based rotaxane. Typically, water-soluble components are prepared, after which the Suzuki coupling reaction in water is used to

• 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

• α-CD-based rotaxane comprising a stilbene axle that was synthesized by the Suzuki coupling reaction to light irradiation (Figure 6, right) [58]. In this structure, α-CD was first located on the trans-stilbene moiety, after which it moved to the benzene ring moiety via the cis-isomerization of the

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• to good yields of the corresponding products. The vinyl boronates obtained from the aforementioned reaction were subsequently subjected to a Suzuki coupling with the remaining aryl iodides obtained from 16 in the presence of a palladium catalyst. This step facilitated the formation of functionalized

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

• further substitution directly on the meso- or a meso-phenyl ortho/meta/para positions of a porphyrin, is the introduction of C–C bond forming chemistry. This is typically achieved using palladium and/or another transition-metal catalyst [20]. Sonagashira [21], Suzuki–Miyaura [22], Heck [23], Stille [24

• coupling reactions, Suzuki–Miyaura couplings are known to be a robust tool when functionalizing porphyrins [29][30]. Many complex porphyrinoid architectures have been synthesized in this manner, from functional porphyrin arrays [31][32][33] to sterically challenging meso-substituted aryl bis-pocket

Synthesis of benzo[f]quinazoline-1,3(2H,4H)-diones

• Ruben Manuel Figueira de Abreu,
• Peter Ehlers and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 2708–2719, doi:10.3762/bjoc.20.228

• and Suzuki–Miyaura cross-coupling reactions followed by Brønsted acid-mediated cycloisomerisation. The developed methodology tolerates various functional groups and leads to moderate up to quantitative yields of the final products. The impact of different functional groups on the optical properties

• known which allow for an individual introduction of substituents at both positions [37][38][51][52][53][54][55][56][57][58][59][60][61]. In our previous work, we developed a new method which enables both positions to be independently functionalised by Sonogashira- and Suzuki–Miyaura cross-coupling

• of palladium-catalysed Sonogashira–Hagihara and Suzuki–Miyaura cross-coupling reactions (Scheme 1). The final cyclisation step is accomplished by an acid-mediated cycloisomerisation. The synthesis of starting materials 4 was carried out by our previously reported protocol [65]. While compounds 4a–f