Recent advances in total synthesis of illisimonin A

• Juan Huang and
• Ming Yang

Beilstein J. Org. Chem. 2025, 21, 2571–2583, doi:10.3762/bjoc.21.199

• Suzuki and co-workers in 2021 [44]. Their work proposed that this core structure could be generated from a highly oxidized allo-cedrane moiety through a tandem retro-Claisen/aldol reaction. Beginning with compound 100, a 6-step sequence afforded ortho-quinone 101 (Scheme 10). Heating 101 promoted an

Comparative analysis of complanadine A total syntheses

• Reem Al-Ahmad and
• Mingji Dai

Beilstein J. Org. Chem. 2025, 21, 2334–2344, doi:10.3762/bjoc.21.178

• reaction to rapidly establish the tetracyclic skeleton of complanadine A and an iridium-catalyzed site-selective pyridine C–H borylation followed by a Suzuki–Miyaura cross coupling to forge the C2–C3’ linkage. Their synthesis achieves a high degree of synergy between classic transformations and modern

• lycodine 34 underwent Ir-catalyzed C3–H borylation mainly guided by steric factors to provide boronic ester 35 in 75% yield. With the boronic ester handle at the C3 position, the subsequent Suzuki–Miyaura cross coupling between 35 and 33 occurred smoothly to deliver pseudo-dimer 36, which upon acidic

• -oxidation at one of the two benzylic positions, they started with benzylic oxidation of 34 using SeO2 to provide 37, which was further oxidized to pyridine N-oxide 38. Treatment of 38 with POCl3 in DMF delivered 2-chloropyridine 39 for the subsequent Suzuki–Miyaura cross coupling with 35 to form the C2–C3

Insoluble methylene-bridged glycoluril dimers as sequestrants for dyes

• Suvenika Perera,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 2302–2314, doi:10.3762/bjoc.21.176

• -surfaces and which are activated for electrophilic aromatic substitution reactions. For the synthesis of W1, we initially prepared tetramethoxybiphenyl 1 (Scheme 1) according to the literature procedure involving the Suzuki coupling between 3,4-dimethoxybromobenzene and 3,4-dimethoxyphenylboronic acid [44

Research towards selective inhibition of the CLK3 kinase

• Vinay Kumar Singh,
• Frédéric Justaud,
• Dabbugoddu Brahmaiah,
• Nangunoori Sampath Kumar,
• Blandine Baratte,
• Thomas Robert,
• Stéphane Bach,
• Chada Raji Reddy,
• Nicolas Levoin and
• René L. Grée

Beilstein J. Org. Chem. 2025, 21, 2250–2259, doi:10.3762/bjoc.21.172

• -bromo-5-chloroaniline (2b). Next, we prepared the final targets by Suzuki-type reactions using the aromatic bromides 7. As indicated before, the acid function designed to interact with the lysine 241 has been introduced both in para and meta positions of the aromatic linker. Further we have prepared two

• series of molecules: the ones without chlorine in meta position on this group (series a) and the others which kept this chlorine, like in DB18 (series b). These syntheses are reported in Scheme 2. A Suzuki-type Pd-catalyzed coupling of 7a with 4-(methoxycarbonyl)phenylboronic acid dimethyl ester (8) gave

The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products

• Dong-Xing Tan and
• Fu-She Han

Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164

• and transformations of 43 produced hydroxyketone 44. Due to the steric hindrance of this substrate, the subsequent Suzuki cross coupling reaction with 3-boronophenol proceeded in low yield. To address this issue, Han′s group employed a novel palladacycle catalyst 45, previously developed by their

• -catalyzed Suzuki cross-coupling reaction of sterically hindered substrates developed by Han [35][36][37], the coupled product 57 was obtained in a satisfactory yield (72%) from 55 and pinacol boronate 56, along with trace amounts of the double bond migrated side product 58 (57:58 = ca. 15:1). Demethylation

• hydroxyketone 104 in excellent diastereoselectivity and enantioselectivity [9][11]. Ozonolysis of the double bond in 104 followed by Purdie methylation with Ag2O/MeI, base-mediated vinyl triflation, and Pd-catalyzed Suzuki–Miyaura cross coupling with pinacol boronate 105 delivered diene 106. Next, The Et2AlCl

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

Aryl iodane-induced cascade arylation–1,2-silyl shift–heterocyclization of propargylsilanes under copper catalysis

• Rasma Kroņkalne,
• Rūdolfs Beļaunieks,
• Armands Sebris,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2025, 21, 1984–1994, doi:10.3762/bjoc.21.154

• propargylsilane 7d halogenation–cyclization cascade and Suzuki–Miyaura cross-coupling in the second step [22]. Thus, we have developed a faster and palladium-free route towards tetrahydrofurans 8. The latter can still be modified further through silicon–halide exchange followed by cross-coupling chemistry as

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