Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• -sensitive substrates. Another challenge, shared with Nicewicz's method [90], is the preparation of arylacridine 159 in a single step from the relatively expensive 9-chloroacridine through Pd-catalyzed cross-coupling with 2-chlorophenylboronic acid. Additionally, for large-scale reactions, a flow reactor is

Sequential hydrozirconation/Pd-catalyzed cross coupling of acyl chlorides towards conjugated (2E,4E)-dienones

• Benedikt Kolb,
• Daniela Silva dos Santos,
• Sanja Krause,
• Anna Zens and
• Sabine Laschat

Beilstein J. Org. Chem. 2023, 19, 176–185, doi:10.3762/bjoc.19.17

• Crombie’s work on dienamides and prepared dienoates 15 by hydrozirconation of terminal alkynes 16 followed by Pd-catalyzed cross coupling with enoates 17 [55][56]. A repetitive approach gave rise to oligoenoates [57]. Hydrozirconations were also combined with carbonylations to install carbonyl groups. For

• -trimethoxybenzoyl chloride (26k), and pentafluorobenzoyl chloride (26l) were also tested, but did not give any trace of the respective dienone 27 (Table 4, entries 9–12). Consequently, the hydrozirconation and Pd-catalyzed cross coupling is rather sensitive towards both electron-donating and electron-withdrawing

• . Hydrozirconation and Pd-catalyzed cross coupling of 25a and 26a with various solvents, reaction times, and temperatures. Hydrozirconation and Pd-catalyzed cross coupling of 25a and 26a by using different Pd catalysts. Hydrozirconation and Pd-catalyzed cross coupling of enyne 25 and acyl-chlorides 26

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• °C and 0 °C, temperatures at which these organometallic reagents are also reported to be quite stable. The zincated dithiins can also be prepared by transmetalation of the magnesiated dithiins at −30 °C, and these organozinc reagents can then be used in room temperature Pd-catalyzed cross-coupling

One-pot synthesis of 2-arylated and 2-alkylated benzoxazoles and benzimidazoles based on triphenylbismuth dichloride-promoted desulfurization of thioamides

• Arisu Koyanagi,
• Yuki Murata,
• Shiori Hayakawa,
• Mio Matsumura and
• Shuji Yasuike

Beilstein J. Org. Chem. 2022, 18, 1479–1487, doi:10.3762/bjoc.18.155

• cyclopropanes with arenes [29]. They have also been used in Pd-catalyzed cross-coupling reactions to react with hypervalent iodonium salts, organostananes, and vinyl epoxides [30][31][32]. Moreover, there are reports of them serving as oxidizing agents for alcohols [33]. Two papers have recently reported

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

• (HRMS). To assess the suitability of the boronic esters 2a and 2b to be used as building blocks in Suzuki–Miyaura reactions, the Pd-catalyzed cross-coupling reaction of norbornadiene 2a and bromobenzene (4a) was examined under different conditions (Table 1, Scheme 2). First experiments were conducted

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

• their optoelectronic properties, the search for new candidates is of ongoing interest. Recently, considerable attention has been given to acridines in our laboratory and we developed new synthetic methods for dibenzoacridines and acridones based on Pd-catalyzed cross-coupling reactions [55][56]. More

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

• hydrolysis using 18% aq HCl furnishing the corresponding aldehyde [21]. Without purification, the resultant aldehyde intermediate was then directly reduced using potassium borohydride to the corresponding primary alcohol 11a in 74% yield starting from 9a. Pd-catalyzed cross-coupling of 11a with pinacol

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

Deoxyfluorination of acyl fluorides to trifluoromethyl compounds by FLUOLEAD^®/Olah’s reagent under solvent-free conditions

• Yumeng Liang,
• Akihito Taya,
• Zhengyu Zhao,
• Norimichi Saito and
• Norio Shibata

Beilstein J. Org. Chem. 2020, 16, 3052–3058, doi:10.3762/bjoc.16.254

• developed various efficient methodologies for the electrophilic [14][15], nucleophilic [16], and radical [17] trifluoromethylation reactions for more than a decade. In recent years, we also reported the direct introduction of an acyl fluoride unit into aromatic compounds by the Pd-catalyzed cross-coupling

Towards triptycene functionalization and triptycene-linked porphyrin arrays

• Gemma M. Locke,
• Keith J. Flanagan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2020, 16, 763–777, doi:10.3762/bjoc.16.70

• evident linearity in these systems. Moreover, initial UV–vis and fluorescence studies show the promise of triptycene as a linker for electron transfer studies, showcasing its isolating nature. Keywords: BODIPY; Pd-catalyzed cross-coupling; porphyrins; Sonogashira cross-coupling; triptycene; Introduction

Starazo triple switches – synthesis of unsymmetrical 1,3,5-tris(arylazo)benzenes

• Andreas H. Heindl and
• Hermann A. Wegner

Beilstein J. Org. Chem. 2020, 16, 22–31, doi:10.3762/bjoc.16.4

• . Synthetic strategy towards 1,3,5-tris(arylazo)benzenes 3 based on consecutive Baeyer–Mills reactions. Preparation of tris(arylazo)benzenes 3 by Pd-catalyzed cross-coupling reactions of N-Boc-arylhydrazides and bromo-substituted ABs, followed by oxidation. Synthesis of azobenzene building block 8. Synthesis

A new approach to silicon rhodamines by Suzuki–Miyaura coupling – scope and limitations

• Thines Kanagasundaram,
• Antje Timmermann,
• Carsten S. Kramer and
• Klaus Kopka

Beilstein J. Org. Chem. 2019, 15, 2569–2576, doi:10.3762/bjoc.15.250

• catalyst, different substituted boroxines were assessed to explore the scope of the Pd-catalyzed cross-coupling reaction. Conclusions: A number of silicon rhodamines were synthesized under the optimized conditions in up to 91% yield without the necessity of HPLC purification. Moreover, silicon rhodamines

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

• -catalyzed cross-coupling reactions have laid down the foundation of new C–C bond formations [50][51]. A number of Pd-catalyzed organic reactions viz., C–N coupling, amination and intramolecular amidation, cyclization, and Suzuki–Miyaura coupling [52][53][54][55] have recently been reported in the literature

• organic reactions. In the syntheses of IPs, various forms of copper viz., salts, complexes, MOFs, oxides, and nanoparticles (NPs) have been used as the catalytic system in both multicomponent reactions (MCRs) as well as derivatization methodologies. The role of palladium in synthetic chemistry Pd

A selective removal of the secondary hydroxy group from ortho-dithioacetal-substituted diarylmethanols

• Anna Czarnecka,
• Emilia Kowalska,
• Agnieszka Bodzioch,
• Joanna Skalik,
• Marek Koprowski,
• Krzysztof Owsianik and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2018, 14, 1229–1237, doi:10.3762/bjoc.14.105

• reactions (e.g., Suzuki–Miyaura, Stille, Kumada, Hiyama or Negishi couplings) play a key role in the preparation of diarylmethanes. However, the reactions involving sulfur-containing moieties have not been reported yet (Scheme 1) [1]. It is noteworthy that under certain conditions, the Pd-catalyzed cross

• -coupling reactions of substrates containing an 1,3-dithiane moiety are feasible, like in the case of the 2-arylation of 2-aryl-substituted 1,3-dithianes. However, in the case of 2-benzyl-substituted 1,3-dithianes, a tandem elimination/1,3-dithiane ring opening followed by a Pd-catalyzed C−S bond formation

Palladium-catalyzed Heck-type reaction of secondary trifluoromethylated alkyl bromides

• Tao Fan,
• Wei-Dong Meng and
• Xingang Zhang

Beilstein J. Org. Chem. 2017, 13, 2610–2616, doi:10.3762/bjoc.13.258

• carried out in 0.2 mmol scale. bEthyl 2,2-difluoro-2-iodoacetate was used. Radical clock experiment for mechanistic studies. Proposed mechanism. Representative results for the optimization of Pd-catalyzed cross-coupling between 1a and 2-bromo-1,1,1-trifluorohexane (2a)a. Radical inhibition experiments of

• Pd-catalyzed cross-coupling between 1a and 2-bromo-1,1,1-trifluorohexane (2a)a. Supporting Information Supporting Information File 400: General experimental information, experimental details on the synthesis of compounds 2–4 and 6; full characterization data as well as 1H/ 19F/ 13C NMR spectra of

An efficient Pd–NHC catalyst system in situ generated from Na₂PdCl₄ and PEG-functionalized imidazolium salts for Mizoroki–Heck reactions in water

• Nan Sun,
• Meng Chen,
• Liqun Jin,
• Wei Zhao,
• Baoxiang Hu,
• Zhenlu Shen and
• Xinquan Hu

Beilstein J. Org. Chem. 2017, 13, 1735–1744, doi:10.3762/bjoc.13.168

• ligands, functionalized with sulfonate- [41][42][43][44][45][46], carboxylate- [47][48][49][50][51][52], polyether- [53][54][55][56][57][58][59] and other hydrophilic groups [60][61][62][63], have been developed and used in the aqueous Pd-catalyzed cross-coupling reactions. Among them, most of them were

• soluble ligands for aqueous organic reactions during the past decades [68][69]. More recently, several PEG-functionalized azolium salts have been synthesized as water soluble NHC precursors for aqueous Pd-catalyzed cross-coupling reactions [56][57][58][59][70]. Fujihara also pointed out that the flexible

Synthesis of tetrasubstituted pyrazoles containing pyridinyl substituents

• Josef Jansa,
• Ramona Schmidt,
• Ashenafi Damtew Mamuye,
• Laura Castoldi,
• Alexander Roller,
• Vittorio Pace and
• Wolfgang Holzer

Beilstein J. Org. Chem. 2017, 13, 895–902, doi:10.3762/bjoc.13.90

• been also observed in the course of related Pd-catalyzed cross-coupling reactions, such as, for instance, in Suzuki–Miyaura reactions [38]. In contrast, the corresponding 2-pyridinyl or 2-thienyl organozinc congeners gave much better results with nearly no homocoupling side reactions and only few

• instance for 2,2’-bipyridines [43][44] and other comparable systems [45]. In Figure 1, complete NMR data for the tetrapyridinylpyrazole 9a are displayed, which permits to follow some of the trends regarding chemical shift considerations discussed above. Conclusion Pd-catalyzed cross-coupling reactions of

Substitution of fluorine in M[C₆F₅BF₃] with organolithium compounds: distinctions between O- and N-nucleophiles

• Anton Yu. Shabalin,
• Nicolay Yu. Adonin and
• Vadim V. Bardin

Beilstein J. Org. Chem. 2017, 13, 703–713, doi:10.3762/bjoc.13.69

• ]. Over the last 15 years, we reported the successful application of polyfluorinated organoborates K[RC6F4BF3], K[C6F5B(OMe)3] and K[CF2=CFBF3] as boron-containing reagents in the Pd-catalyzed cross-coupling reactions with C-electrophiles [22][23][24][25][26][27]. Nowadays a common approach to these

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• with copper cation in comparison to bidentate ligands 5c and 5d. However, the cholane skeleton in 5c and 5d can be useful for integration of these ligands into lipophilic membranes. Conclusion Cu- and Pd-catalyzed cross-coupling reactions were applied for the preparation of arylamino derivatives of

Efficient access to β-vinylporphyrin derivatives via palladium cross coupling of β-bromoporphyrins with N-tosylhydrazones

• Vinicius R. Campos,
• Ana T. P. C. Gomes,
• Anna C. Cunha,
• Maria da Graça P. M. S. Neves,
• Vitor F. Ferreira and
• José A. S. Cavaleiro

Beilstein J. Org. Chem. 2017, 13, 195–202, doi:10.3762/bjoc.13.22

• such synthetic methodology in porphyrin chemistry allowing the synthesis of new derivatives, containing β-arylvinyl substituents. Keywords: N-tosylhydrazones; Pd-catalyzed cross coupling; porphyrins; Introduction Porphyrin-type heterocycles are well known for their special role in several scientific

• File 1). Conclusion In summary, we have reported the efficient synthesis of new β-alkenyl-type porphyrin derivatives through Pd-catalyzed cross-coupling reaction of β-bromoporphyrinatozinc(II) complex with N-tosylhydrazones. The best conditions for the reaction of 2-bromo-5,10,15,20

Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

• Mizuki Yamada,
• Mio Matsumura,
• Yuki Uchida,
• Masatoshi Kawahata,
• Yuki Murata,
• Naoki Kakusawa,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2016, 12, 1309–1313, doi:10.3762/bjoc.12.123

• organoantimony compounds in organic synthesis has attracted much interest during the last two decades [25][26]. Trivalent organoantimony compounds (stibanes) such as aryl- and ethynylstibanes are useful transmetalation agents in Pd-catalyzed cross-coupling reactions with aryl halides and acyl chlorides [27][28

Spiro-fused carbohydrate oxazoline ligands: Synthesis and application as enantio-discrimination agents in asymmetric allylic alkylation

• Jochen Kraft,
• Martin Golkowski and
• Thomas Ziegler

Beilstein J. Org. Chem. 2016, 12, 166–171, doi:10.3762/bjoc.12.18

• substitution using similar PyOx ligands are currently under investigation and will be published elsewhere. Pd-catalyzed cleavage of spiro-bis(isooxazoline) ligand A to isoxazole B and Pd-complex D prepared from spiro-oxazoline C. Synthesis of 2-benzylsulfanyl-1,3-oxazolines 7 and 8. Pd-catalyzed cross coupling

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• ketone. Protection of the indole nitrogen was not necessary and 5 was obtained as a bright yellow solid in excellent yield (Scheme 1). The route appears more efficient than earlier procedures via 6-formylindoles [13][14][15]. There have been only few Pd-catalyzed cross-coupling reactions of unprotected 6

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation

• Vadim V. Bardin,
• Anton Yu. Shabalin and
• Nicolay Yu. Adonin

Beilstein J. Org. Chem. 2015, 11, 608–616, doi:10.3762/bjoc.11.68

• of Catalysis, SB RAS, Acad. Lavrentjev Ave. 5, Novosibirsk, 630090, Russian Federation 10.3762/bjoc.11.68 Abstract Small differences in the reactivity of weakly nucleophilic potassium aryltrifluoroborates are revealed in the silver-assisted Pd-catalyzed cross-coupling of K[4-RC6F4BF3] (R = H, Bu

• reported by Kishi et al. [16] for the cross-coupling of alkenylboronic acids with alkenyl iodides in the presence of Ag2O and elucidated by formation of AgOH which acts like aqueous KOH or TlOH. Korenaga et al. [20] have studied Pd-catalyzed cross-coupling of C6F5B(OH)2 with aryl halides in the presence of

• anhydrous THF in the presence of trialkylamine as a base or in alcohols [4]. Alternatively, the Pd-catalyzed cross-coupling of K[ArBF3] in aqueous THF is proved to proceed through stepwise hydrolysis to produce more reactive [ArBFn(OH)3-n]− or ArB(OH)2 [35][38]. However, special experiments showed that K

An improved procedure for the preparation of Ru(bpz)₃(PF₆)₂ via a high-yielding synthesis of 2,2’-bipyrazine

• Danielle M. Schultz,
• James W. Sawicki and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2015, 11, 61–65, doi:10.3762/bjoc.11.9

• reaction, we turned our attention towards the use of more reactive aryl iodides. A screen of solvents commonly used in Pd-catalyzed cross-coupling reactions revealed that DMF provided the highest yields (Table 1, entries 3–5). We next examined the effect of varying equivalents of the terminal reductant