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

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

• 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

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

• previously by other groups [38][39], however, we here use a different protocol. Intermediates 25 or 26 were reacted in Suzuki–Miyaura couplings [36] with commercially available methyl 5-bromo-2-iodobenzoate [40], to obtain the key intermediate dimethyl 6,6’-(dithieno[3,2-b:2’,3’-d]thiophene-2,6-diyl)bis(3

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, whose reactivity in Suzuki–Miyaura couplings has not been investigated, so far [32][33]. To explore the suitability of borylated norbornadienes for Suzuki–Miyaura coupling reactions and thus to provide new useful building blocks for the modular construction of norbornadiene derivatives

Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions for the synthesis of chiral biaryl compounds with a large steric substituent at the 2-position

• Yongsu Li,
• Bendu Pan,
• Xuefeng He,
• Wang Xia,
• Yaqi Zhang,
• Hao Liang,
• Chitreddy V. Subba Reddy,
• Rihui Cao and
• Liqin Qiu

Beilstein J. Org. Chem. 2020, 16, 966–973, doi:10.3762/bjoc.16.85

• Abstract Pd-catalyzed asymmetric Suzuki–Miyaura couplings of 3-methyl-2-bromophenylamides, 3-methyl-2-bromo-1-nitrobenzene and 1-naphthaleneboronic acids have been successfully developed and the corresponding axially chiral biaryl compounds were obtained in very high yields (up to 99%) with good

• bromobenzene substrates and the Pd···O interaction between carbonyl and palladium seem essential to achieve high enantioselectivity. Keywords: asymmetric catalysis; biaryls; monophosphine ligand; palladium catalyst; Suzuki–Miyaura couplings; Introduction Axially chiral molecules have received much attention

• efficient synthesis of this scaffold [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22], like Hiyama [23][24], Negishi [25][26] or Suzuki–Miyaura couplings [27][28][29][30][31][32][33][34][35][36]. In these synthetic strategies, the reaction system of palladium with chiral phosphine ligands was

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

• Md. Shafiqur Rahman and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

• via 1,4-cobalt migration. The resulting 7-hydroxybenzo[b]phosphole derivative was used for further π-extension through Suzuki–Miyaura couplings and a Scholl reaction, the latter closing the triphenylene ring. The absorption and emission spectra of the thus-synthesized compounds illustrated their

• converted to the triflate, and subjected to Suzuki–Miyaura couplings with 2-bromophenylboronic acid (5a) or 3-bromonaphth-2-ylboronic acid (5b) to afford the phosphole-fused biaryls 6a and 6b, respectively, in decent yields. Subsequent Suzuki–Miyaura couplings of 6a or 6b with 3,4-dialkoxyarylboronic acids

Palladium-catalyzed synthesis and nucleotide pyrophosphatase inhibition of benzo[4,5]furo[3,2-b]indoles

• Hoang Huy Do,
• Saif Ullah,
• Alexander Villinger,
• Joanna Lecka,
• Jean Sévigny,
• Peter Ehlers,
• Jamshed Iqbal and
• Peter Langer

Beilstein J. Org. Chem. 2019, 15, 2830–2839, doi:10.3762/bjoc.15.276

• diindolofurans by regioselective Suzuki–Miyaura couplings of tetrabromofuran and subsequent cyclization by tetrafold Buchwald–Hartwig reaction [31]. We also studied the synthesis of benzo[4,5]furo[3,2-b]indoles by a similar concept. However, while performing our studies, Truong et al. reported the synthesis of

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• reference [67]. Suzuki−Miyaura couplings with, or without, ppm Pd. Conditions: ArI 0.5 mmol 3a, Ar’B(OH)2 (0.75–1.00 mmol, 1.5–2.0 equiv) 3b, *with 200 ppm of Pd(OAc)2. Adapted from reference [70]. Copyright 2016 American Chemical Society. Cascade reaction with GOx and Myo. Adapted from reference [82

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

• Katharina Hiebler,
• Georg J. Lichtenegger,
• Manuel C. Maier,
• Eun Sung Park,
• Renie Gonzales-Groom,
• Bernard P. Binks and
• Heidrun Gruber-Woelfler

Beilstein J. Org. Chem. 2018, 14, 648–658, doi:10.3762/bjoc.14.52

• oxide Ce0.99Pd0.01O2–δ showed to be least efficient for the explored Suzuki–Miyaura couplings. Regarding the selectivity of the catalysts in the selected cross-coupling reactions, no bromoarene-deriving side products (dehalogenation product Ar’ and bromoarene homocoupling product Ar’Ar’) could be

• of the catalytic active compounds. To assess the reusability of the heterogeneous catalysts, the Pd-substituted metal oxides were subjected to Suzuki–Miyaura couplings of 4-bromotoluene with phenylboronic acid in five subsequent reactions, i.e., after one reaction was finished, the particles were

• activities for Suzuki–Miyaura couplings in batch [37] and continuous flow [38]. After milling, the coarse and fine fractions of the particles were separated via sedimentation. For this purpose, 2 g of catalyst were suspended in 1 L water, the particles were de-aggregated by ultrasonic treatment and left to

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η⁵-Cp)Pd(IPr)Cl with (η³-cinnamyl)Pd(IPr)(Cl) and (η³-1-t-Bu-indenyl)Pd(IPr)(Cl)

• Patrick R. Melvin,
• Nilay Hazari,
• Hannah M. C. Lant,
• Ian L. Peczak and
• Hemali P. Shah

Beilstein J. Org. Chem. 2015, 11, 2476–2486, doi:10.3762/bjoc.11.269

• preliminary reports indicate that (η5-Cp)Pd(NHC)(Cl) precatalysts are highly active. For example, full conversion at room temperature was achieved using simple aryl chlorides as the substrate in Suzuki–Miyaura couplings at relatively low catalyst loadings (1 mol %) [18]. However, despite this impressive

Extending the utility of [Pd(NHC)(cinnamyl)Cl] precatalysts: Direct arylation of heterocycles

• Anthony R. Martin,
• Anthony Chartoire,
• Alexandra M. Z. Slawin and
• Steven P. Nolan

Beilstein J. Org. Chem. 2012, 8, 1637–1643, doi:10.3762/bjoc.8.187

• ) (Figure 1). Complexes 1 and 2 are commercially available and have proven to be highly efficient in Suzuki–Miyaura coupling and Buchwald–Hartwig amination reactions [17][18][19][20]. We have also evaluated the recently reported [Pd(IPr*)(cin)Cl] (3), which has shown potency in Suzuki–Miyaura couplings [21

A short and efficient synthesis of valsartan via a Negishi reaction

• Samir Ghosh,
• A. Sanjeev Kumar and
• G. N. Mehta

Beilstein J. Org. Chem. 2010, 6, No. 27, doi:10.3762/bjoc.6.27

• synthesis of sartans: whilst the synthesis of losartan [4] as described in the literature makes use of Negishi [5][6] and Ullmann [7] couplings, the published methods for the preparation of valsartan utilize Suzuki–Miyaura couplings [8]. Of these, Negishi reactions have proved to be very efficient. However