Total synthesis of insect sex pheromones: recent improvements based on iron-mediated cross-coupling chemistry

• Eric Gayon,
• Guillaume Lefèvre,
• Olivier Guerret,
• Adrien Tintar and
• Pablo Chourreu

Beilstein J. Org. Chem. 2023, 19, 158–166, doi:10.3762/bjoc.19.15

• reactions, which witnessed considerable development in the last two decades [14], several cross-coupling methodologies involving soft nucleophiles, such as iron-mediated Suzuki–Miyaura cross-couplings, being reported [15]. The introduction of alkyl–alkenyl linkage by means of iron-catalyzed cross-coupling

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

• substitution for the minimization of 1,3-allylic strain to enable Suzuki coupling for biaryl formation as a single atropisomer. The optimized conditions for this transformation utilize Buchwald’s catalyst (SPhos and Pd-based G2 precatalyst) in conjunction with K3PO4. With DBCOD bearing carboxylic acid handles

Inline purification in continuous flow synthesis – opportunities and challenges

• Jorge García-Lacuna and
• Marcus Baumann

Beilstein J. Org. Chem. 2022, 18, 1720–1740, doi:10.3762/bjoc.18.182

• obtain the pure compound that met the requirements (>99.5%) [41]. Another very recent report which couples a Suzuki–Miyaura reaction with inline purification, uses capture-SMB technology as its purification approach [42] (Table 2, entry 2). The crude material is directed into two twin C-18 columns that

• reported by Pitts and collaborators. This study achieves full removal of metal species after common homogenous catalytic reactions such as a Suzuki–Miyaura reaction, Sonogashira reaction or hydrogenation mediated by Wilkinson’s catalyst [84]. Other interesting examples to remove transition metals in

• successfully coupled to a Suzuki–Miyaura reaction [119]. Crystallization was identified as a suitable purification technique to separate products from unreacted starting materials while avoiding metal contamination. Water was used as antisolvent and two mixing units were needed in the crystallization process

Total synthesis of grayanane natural products

• Nicolas Fay,
• Rémi Blieck,
• Cyrille Kouklovsky and
• Aurélien de la Torre

Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181

• diastereoselectivity in 58% on a 3 g scale. Subsequently, vinyl halide 48 was converted to diene 50 by Suzuki coupling with potassium vinyltrifluoroborate (49) in 90% yield (Scheme 8). The C7–C8 bond formation from a bridgehead carbocation was a real challenge to close the 7-membered ring. To achieve this, the

Simple synthesis of multi-halogenated alkenes from 2-bromo-2-chloro-1,1,1-trifluoroethane (halothane)

• Yukiko Karuo,
• Atsushi Tarui,
• Kazuyuki Sato,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2022, 18, 1567–1574, doi:10.3762/bjoc.18.167

• presence of KOH. In this reaction, halothane plays a key role in the construction of highly halogenated and structurally intriguing products. The tri-halogenated alkenyl ether has potential applications in organic chemistry, e.g., in Suzuki–Miyaura or Sonogashira cross-coupling reactions. Further

Electrogenerated base-promoted cyclopropanation using alkyl 2-chloroacetates

• Kouichi Matsumoto,
• Yuta Hayashi,
• Kengo Hamasaki,
• Mizuki Matsuse,
• Hiyono Suzuki,
• Keiji Nishiwaki and
• Norihito Kawashita

Beilstein J. Org. Chem. 2022, 18, 1116–1122, doi:10.3762/bjoc.18.114

• Kouichi Matsumoto Yuta Hayashi Kengo Hamasaki Mizuki Matsuse Hiyono Suzuki Keiji Nishiwaki Norihito Kawashita Department of Chemistry, School of Science and Engineering, Kindai University 3-4-1 Kowakae, Higashi-osaka, Osaka 577-8502, Japan Department of Pharmaceutical Sciences, Faculty of Pharmacy

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

• [34], dibromodithienothiophene 24 is lithiated with n-butyllithium at −90 °C, and the resulting species is reacted in situ with triisopropyl borate. After aqueous workup, dithieno[3,2-b:2’,3’-d]thiophene-2,6-diylboronic acid (25) is obtained, enabling subsequent Suzuki–Miyaura cross-coupling [36

• 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

• Information File 1. According to the literature [41], Aliquat 336® can be added to Suzuki–Miyaura reactions. Here, this did not improve the yield, but decreased its fluctuation from batch to batch. After sufficient amounts of intermediate 27 were isolated, attempts for ring-closure were made. Initial attempts

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

• transformations. Thus far, mechanochemical palladium-catalyzed cross-coupling reactions such as Suzuki–Miyaura [34][35][36][37][38][39][40][41][42][43][44][45][46][47], Buchwald–Hartwig [48][49][50][51][52], Sonogashira [53][54][55][56], Negishi [57], Mizoroki–Heck [58][59][60], and C–S bond-forming [61

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

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• flow conditions. In these reactions, the leaching of palladium was as low as 34 ppm for Suzuki–Miyaura reactions and 100 ppm for Heck reactions. Importantly, the functionalized nanoparticles could be reused several times without observing a decrease in catalytic activity. 3.2.4 Multistep processes: The

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

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• stapling techniques to stabilise α-helical secondary structure motifs of peptides led to the design of modulators of protein–protein interactions, which had been considered undruggable for a long time. We disclose a novel approach towards peptide stapling utilising macrocyclisation by late-stage Suzuki

• its native binding partner β-catenin. An increased proteolytic stability against proteinase K has been demonstrated. Keywords: accelerated molecular dynamics; halotryptophan; intrinsically disordered peptides; late-stage diversification; macrocyclisation; molecular dynamics; stapled peptides; Suzuki

• ]. Additionally, halotryptophans were incorporated in pentapeptides as building blocks for macrocyclisation by Suzuki–Miyaura cross-coupling (SMC) aiming at the preparation of bicyclic peptides [71]. Recently, intramolecular SMC has been successfully applied to side chain-to-tail cyclisation between

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode

• Ettore Crovini,
• Zhen Zhang,
• Yu Kusakabe,
• Yongxia Ren,
• Yoshimasa Wada,
• Bilal A. Naqvi,
• Prakhar Sahay,
• Tomas Matulaitis,
• Stefan Diesing,
• Ifor D. W. Samuel,
• Wolfgang Brütting,
• Katsuaki Suzuki,
• Hironori Kaji,
• Stefan Bräse and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2021, 17, 2894–2905, doi:10.3762/bjoc.17.197

• Ettore Crovini Zhen Zhang Yu Kusakabe Yongxia Ren Yoshimasa Wada Bilal A. Naqvi Prakhar Sahay Tomas Matulaitis Stefan Diesing Ifor D. W. Samuel Wolfgang Brutting Katsuaki Suzuki Hironori Kaji Stefan Brase Eli Zysman-Colman Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of

Synthesis of highly substituted fluorenones via metal-free TBHP-promoted oxidative cyclization of 2-(aminomethyl)biphenyls. Application to the total synthesis of nobilone

• Ilya A. P. Jourjine,
• Lukas Zeisel,
• Jürgen Krauß and
• Franz Bracher

Beilstein J. Org. Chem. 2021, 17, 2668–2679, doi:10.3762/bjoc.17.181

• frequently and at various positions in fluorenones from nature. The model cyclization precursors were prepared in two step syntheses by Suzuki coupling [58] of commercially available ortho-substituted areneboronic acids 7 and bromobenzenes 6, 12, and 13 followed by either reductive amination [59] in the case

• aryllithium intermediate. For the synthesis of the benzylamine unit, commercially available nitrile 19 was reacted with NBS to regioselectively introduce a bromo substituent to give bromobenzonitrile 20 in a yield of 51% [65]. Biaryl 21 was constructed via a Suzuki coupling [57] of 18 and 20 in 41% yield. As

• expected, the TBS ether was cleaved under the Suzuki conditions and had to be reapplied [63] to give bis-TBS-protected cyanobiaryl 22 in 85% yield. Next, the nitrile group was reduced to the corresponding primary amine 23 in 80% yield, using LAH and AlCl3 [60]. The target compound nobilone (1d) was

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

• 43 Prague 2, Czech Republic 10.3762/bjoc.17.179 Abstract The stereoselective Suzuki–Miyaura cross-coupling of (Z)-β-enamido triflates is demonstrated. Depending on the nature of the ligand in the palladium catalyst, either retention or inversion of the configuration during the synthesis of β,β

• -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

• bond of vinyl (pseudo)halides during the Suzuki coupling have been published [25][26][27][28][29]. Typically, inversion of configuration occurs on substrates containing a double bond in conjugation with an electron-withdrawing group, such as the carbonyl group in enones [27][30]. We hypothesized that

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

• /bjoc.17.162 Abstract A facile synthesis of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridine derivatives is reported which is based on POCl3-mediated cyclodehydration followed by double Suzuki–Miyaura cross-coupling. The absorption and fluorescence properties of the obtained products were investigated and

• 3,5-dibromoanthranilic acid (1) [61] with cyclohexanone in POCl3 through an adapted reported procedure [62] (Scheme 1). With precursor 2 in hand, we intended to expand the π-conjugation of the tetrahydroacridine core by adding diversely substituted aryl groups using the Suzuki–Miyaura cross-coupling

• 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

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

• ], rhodium-mediated alkyne [2 + 2 + 2] cycloaddition reactions [3], and the palladium-catalysed aerobic domino Suzuki coupling/Michael addition reaction [4]. The most attractive and common strategies to phenanthridines rely on intramolecular cyclizations of various ortho-functionalized biaryl precursors

• substituents in a range of positions. In all cases at least one methoxy substituent was positioned ortho- to the biaryl axis. The other aromatic ring had to contain an oxime ester, which would form an iminyl electron donor, as shown in Scheme 2. As illustrated substrates 13a–f were accessed using the Suzuki

• 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

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• a reliable strategy in modern organic synthesis. Palladium-catalyzed cross-coupling reactions such as Mizoroki–Heck [5][6][7][8], Suzuki–Miyaura [9][10][11], Buchwald–Hartwig [12][13], Negishi [14][15], Migita–Stille [16], Sonogashira [17], among others [18][19][20], significantly changed the design

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

• -azulene) units capable of absorbing in the near IR region (1.0 to 2.5 μm). Their synthetic strategy involved employing 1,3-dibromo-[2-(3-dodecylthien-2-yl)]azulene (46) as a key precursor and Suzuki and Stille cross-coupling reactions as polymerization tools. The polymer 50 was synthesized from the 1,3

• -dibromo-[2-(3-dodecylthien-2-yl)]azulene (46) by using two successive Suzuki coupling reactions with thiophene boron ester 47 and biphenyl-4,4’-diboronic acid bis(pinacol) ester 49 (Scheme 11), whereas the Suzuki coupling of 46 with 2,1,3-benzothiadiazole-4,7-bis(boronic acid pinacol ester) 51 yielded the

• 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

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 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

• 3-amino-2-naphthoic acid (97) to a Sandmeyer reaction and obtained 98. Then, a Curtius rearrangement of 98 by using diphenylphosphoryl azide (DPPA) yielded 3-iodonaphthalen-2-amine, that was subjected to a Suzuki cross-coupling with potassium vinyltrifluoroborate resulting in aminostyrene 99. The

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• 134 were used as starting material in the Sonogashira and Suzuki reactions. The Sonogashira−Hagihara cross-coupling led to alkynylation at position 5 of the triazole ring in the presence of CuI and Pd(PPh3)4 as catalytic system as well as K3PO4 as base in THF as solvent at 65 °C. However, the Suzuki

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

• components of the OSC. The synthesis of such compounds is also based on the Suzuki coupling reaction between alkylated 6,6’-dibromoisoindigos and corresponding arylboronic derivatives, leading to the formation of target molecules in moderate yield (Scheme 11). In these compounds, the triarylamine substituent

• [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