Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• final Mizoroki–Heck reaction will be discussed in the following section. The Buchwald group [59] reported a ligand-controlled divergent synthesis involving intramolecular cyclisation, allowing for the formation of several heterocycles, including dibenzo[b,f]azepines 89, in two steps. Screening of

• dibenzoazepines 62. Double Buchwald–Hartwig amination towards 10,11-dihydro-5H-dibenzo[b,f]azepine derivatives 71. One-pot Suzuki coupling–Buchwald–Hartwig amination. One-pot Rh/Pd-catalysed synthesis of dihydropyridobenzazepines. A retrosynthetic pathway to dibenzo[b,f]azepines via Mizoroki–Heck reaction. One

• -pot domino Pd-catalyzed Mizoroki–Heck–Buchwald–Hartwig synthesis of dibenzo[b,f]azepines. Dibenzo[b,f]thiapine and -oxepine synthesis via SNAr (thio)etherification, Wittig methylenation and Mizoroki–Heck reaction. A retrosynthetic pathway to dibenzo[b,f]oxepines via Ullmann coupling. Ullmann-type

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• Mizoroki–Heck reaction: construction of the [5-8] bicyclic ring system of brachialactone A study of the versatility of the Mizoroki–Heck reaction in an intramolecular version was recently described by Nishikawa to elaborate the eight-membered ring of brachialactone (7) (fusicoccane series) from an advanced

Suzuki–Miyaura cross coupling is not an informative reaction to demonstrate the performance of new solvents

• James Sherwood

Beilstein J. Org. Chem. 2020, 16, 1001–1005, doi:10.3762/bjoc.16.89

• the key fundamental principles of boron and palladium speciation and the role of the base in the Suzuki–Miyaura reaction. For researchers developing safer solvents, the Mizoroki–Heck reaction is a more suitable cross-coupling methodology to demonstrate solvent performance [28]. The reaction kinetics

• Mizoroki–Heck reaction and hence there is also a motivation to investigate safer alternative solvents that the Suzuki–Miyaura reaction lacks. If researchers are still compelled to study the utility of solvents in the Suzuki–Miyaura reaction, I encourage future studies to be directed at challenging

Functionalization of the imidazo[1,2-a]pyridine ring in α-phosphonoacrylates and α-phosphonopropionates via microwave-assisted Mizoroki–Heck reaction

• Damian Kusy,
• Agata Wojciechowska,
• Joanna Małolepsza and
• Katarzyna M. Błażewska

Beilstein J. Org. Chem. 2020, 16, 15–21, doi:10.3762/bjoc.16.3

• ]pyridine ring has been synthesized via the microwave-assisted Mizoroki–Heck reaction. The efficient modification of the imidazo[1,2-a]pyridine ring has been achieved as late-stage functionalization, enabling and accelerating the generation of a library of compounds from a common precursor. Keywords: α

• -phosphonoacrylates; α-phosphonopropionates; imidazo[1,2-a]pyridine; microwave-assisted reaction; Mizoroki–Heck reaction; Introduction In the last few decades, the Mizoroki–Heck reaction has become one of the main tools in organic synthesis. Its use for the functionalization of a wide range of compounds cannot be

• confirmed by the presence in a number of pharmaceuticals [2][3]. The imidazo[1,2-a]pyridine-ring modification via Pd-catalyzed reactions is broadly reported in the literature [3], however, such functionalizations for more complex molecules are not very common. On the other hand, the Mizoroki–Heck reaction

Bromide-assisted chemoselective Heck reaction of 3-bromoindazoles under high-speed ball-milling conditions: synthesis of axitinib

• Jingbo Yu,
• Zikun Hong,
• Xinjie Yang,
• Yu Jiang,
• Zhijiang Jiang and
• Weike Su

Beilstein J. Org. Chem. 2018, 14, 786–795, doi:10.3762/bjoc.14.66

• highly efficient route for the synthesis of axitinib. Keywords: axitinib; ball-milling; dehalogenation; Heck reaction; indazoles; Introduction The palladium-catalyzed vinylation of alkenes in the presence of a base, known as the Heck reaction (Mizoroki–Heck reaction), is one of the most important

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CF₃SO₂Cl

• Hélène Chachignon,
• Hélène Guyon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273

• (CF3SO2)2Zn, which demonstrated great efficiency in introducing the CF3 moiety on (hetero)aromatic rings [34]. Trifluoromethylation of olefins: In 2005, Vogel and co-workers showed that terminal alkenes could be trifluoromethylated by means of CF3SO2Cl via a palladium-catalysed desulfitative Mizoroki–Heck

• reaction, in classical solvents or in an ionic liquid media, to yield the corresponding CF3 alkenes (Scheme 28) [35][36]. As for Yu, Zhang and co-workers, they described the trifluoromethylation of two enamides under photocatalytic conditions, using similar conditions as those they proposed for the

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• . Easy purification procedures, towards quantitative conversion and minimum byproducts are additionally considered to be major significance to this method. Tullberg et al. investigated the Mizoroki–Heck reaction between iodobenzene and the methyl ester of N-Boc-protected aminoacylate under different

• ]. Mechanochemical Pd-catalyzed C–H activation [185]. Mechanochemical Csp2–H bond amidation using Rh catalyst. Mechanochemical synthesis of indoles using Rh catalyst [187]. Mizoroki–Heck reaction of aminoacrylates with aryl halide in a ball-mill [58]. IBX under mechanomilling conditions [8]. Thiocarbamoylation 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

• 10,000. Keywords: aqueous homogeneous catalysis; Mizoroki–Heck reaction; Na2PdCl4; PEG-functionalized imidazolium salts; Introduction Nowadays, both increasing environmental concerns and drastic commercial competition are the driving forces to develop more sustainable and economic processes for

An effective Pd nanocatalyst in aqueous media: stilbene synthesis by Mizoroki–Heck coupling reaction under microwave irradiation

• Carolina S. García,
• Paula M. Uberman and
• Sandra E. Martín

Beilstein J. Org. Chem. 2017, 13, 1717–1727, doi:10.3762/bjoc.13.166

• make this protocol a great option for stilbene syntheses by Mizoroki–Heck reaction. Keywords: aqueous reaction medium; MAOS; Mizoroki–Heck reaction; Pd nanoparticle; sustainable organic synthesis; Introduction Palladium-catalyzed reactions have emerged as an important tool for organic synthesis

• both coupling partners. The Mizoroki–Heck reaction and related chemistry occupy a special place among the basic types of Pd-catalyzed reactions, particularly the vinylation of aryl/vinyl halides or triflates [7][8][9][10], explored not only in the inter- and intramolecular version [2][11][12][13], but

• also in domino [14] and asymmetric catalytic processes [15]. Due to its versatility, the Mizoroki–Heck reaction is extensively employed in the synthesis of pharmaceutical, agrochemical and natural products, and continues to attract attention within the synthetic chemists’ community [16][17][18]. From

A strategic approach to [6,6]-bicyclic lactones: application towards the CD fragment of DHβE

• Tue Heesgaard Jepsen,
• Emil Glibstrup,
• François Crestey,
• Anders A. Jensen and
• Jesper Langgaard Kristensen

Beilstein J. Org. Chem. 2017, 13, 988–994, doi:10.3762/bjoc.13.98

• chloroformate provided alkyne 22 in 72% yield which reacted with LiI in acetic acid furnishing the desired (Z)-vinyl iodide 23 in 79% isolated yield. A concise screening of the Mizoroki–Heck reaction conditions (which involved Jeffery conditions [23], Pd2dba3/Xantphos [24] or Fu’s salt [25], and PdCl2(PPh3)2 in

A selective and mild glycosylation method of natural phenolic alcohols

• Mária Mastihubová and
• Monika Poláková

Beilstein J. Org. Chem. 2016, 12, 524–530, doi:10.3762/bjoc.12.51

• ]. Isoconiferin (3) has been prepared mainly by the trichloroacetimidate method [20][21] using 4-O-acetylated coniferyl alcohol as the acceptor. On the other hand, the Mizoroki–Heck reaction of 4-hydroxy-3-methoxyphenylboronic acid and peracetylated allyl β-D-glucoside has been used to synthesize 3 in 52% yield

Intramolecular carbonickelation of alkenes

• Rudy Lhermet,
• Muriel Durandetti and
• Jacques Maddaluno

Beilstein J. Org. Chem. 2013, 9, 710–716, doi:10.3762/bjoc.9.81

• development of palladium chemistry [4]. The catalytic cycle starts with the oxidative addition of Pd(0) to generate a σ-arylpalladium(II), then a rapid insertion of a double or triple bond takes place [5]. This method was particularly applied in the “Mizoroki–Heck reaction” [6] for the synthesis of

N-Heterocyclic carbene–palladium(II)-1-methylimidazole complex catalyzed Mizoroki–Heck reaction of aryl chlorides with styrenes

• Ting-Ting Gao,
• Ai-Ping Jin and
• Li-Xiong Shao

Beilstein J. Org. Chem. 2012, 8, 1916–1919, doi:10.3762/bjoc.8.222

• )-Im] complex 1 was found to be an effective catalyst for the Mizoroki–Heck reaction of a variety of aryl chlorides with styrenes. Both activated and deactivated aryl chlorides work well to give the corresponding coupling products in good to excellent yields by using tetrabutylammonium bromide (TBAB

• ) as the ionic liquid. Keywords: aryl chloride; Mizoroki–Heck reaction; N-heterocyclic carbene; palladium complex; synthetic method; Introduction The palladium-catalyzed reaction between organic halides and alkenes, the Mizoroki–Heck reaction, is one of the most versatile methods for the formation of

• carbon–carbon bonds [1][2][3][4][5][6][7]. Usually, in order to achieve the highest efficiency of the palladium-catalyzed Mizoroki–Heck reaction, toxic, air-sensitive and expensive phosphine ligands are introduced to facilitate the corresponding transformations [8][9]. In order to overcome the drawbacks

Unusual behavior in the reactivity of 5-substituted-1H-tetrazoles in a resistively heated microreactor

• Bernhard Gutmann,
• Toma N. Glasnov,
• Tahseen Razzaq,
• Walter Goessler,
• Dominique M. Roberge and
• C. Oliver Kappe

Beilstein J. Org. Chem. 2011, 7, 503–517, doi:10.3762/bjoc.7.59

• of 1.0 mm i.d. coil) was “loaded” with Pd by processing ≈2 mL of the Mizoroki–Heck reaction mixture through the coil under reaction conditions (180 °C, 1.6 mL/min flow rate) with 1 mol % of the Pd(OAc)2 as pre-catalyst. As expected, the desired product 14 was obtained in 94% isolated yield after

• relatively low (Table 2, entries 1 and 2), significantly higher levels of Pd were found in samples derived from the Mizoroki–Heck reaction mixture (Table 2, entry 3). These results, both in terms of decreasing conversion and Pd leaching are therefore analogous to the experiments using Pd/C as a heterogeneous

• . Only renewed loading of the coil by running a Mizoroki–Heck reaction with Pd(OAc)2 or by simply processing a Pd(OAc)2 solution through the coil at elevated temperature regenerated the “palladated” stainless steel coils. Influence of pressure on reaction rate in flow reactors In the resistively heated