Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• reaction in the following order: phase-transfer catalysis, Henry reaction, Suzuki–Miyaura cross-coupling and Tsuji–Trost allylic substitution, hydrogenation, Michael addition, aldol and multicomponent Biginelli reactions, epoxidation, Meerwein−Ponndorf−Verley reduction, aza-Diels−Alder and epoxide ring

• . The low enantioselectivities obtained were mainly attributed to the high flexibility of catalytic amino groups of N,O-type enantiomers. Suzuki–Miyaura cross–coupling and Tsuji–Trost allylic substitution reaction Manoury et al. described the synthesis of ferrocene-bearing enantiomerically pure

• calixarenes and their catalytic performances in the asymmetric Suzuki–Miyaura coupling and Tsuji–Trost allylic alkylation reactions (Scheme 7) [42]. Calix[4]arene mono and dithiophosphines 24–26 were efficiently synthesized from p-tert-butylcalix[4]arene by a one pot Mitsunobu alkylation using

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• group can be easily substituted by an aryl group using a Suzuki–Miyaura cross-coupling reaction. In those cases when a trimethylsilyl group (R4) is also present, it can be removed by TBAF-mediated protodesilylation to give a 1,4,5-trisubstituted pyrazole. It is worth noting that the parent 4,4,5,5

Atom-economical group-transfer reactions with hypervalent iodine compounds

• Andreas Boelke,
• Peter Finkbeiner and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108

• iodoarenes 32. These species smoothly underwent subsequent Suzuki–Miyaura, Sonogashira and Mirozoki–Heck couplings. The respective arylated, alkynylated and alkenylated products 33a–d were obtained in high yields with excellent stereoselectivity. Due to the intramolecular pathway of the first step, high AE

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

Rhodium-catalyzed C–H functionalization of heteroarenes using indoleBX hypervalent iodine reagents

• Erwann Grenet,
• Ashis Das,
• Paola Caramenti and
• Jérôme Waser

Beilstein J. Org. Chem. 2018, 14, 1208–1214, doi:10.3762/bjoc.14.102

• ), which ends up on the pyridinone ring. As alternative, a Suzuki–Miyaura coupling between 3-halogenoindoles and (2-methoxypyridyl)boronic acids followed by a deprotection of the methoxy group [7][8] or transition-metal-catalyzed annulation methods [9] have also been reported. In contrast, several

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

• Pd catalyst together with a PAA (poly(acrylic acid)) based polymer self-assembled in water [32]. The catalytic activity of the nanostructures was compared to the results achieved with the small molecule analogues of the pincer Pd complex, in a Suzuki–Miyaura coupling. When the reaction of vinyl

• 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

• development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki–Miyaura cross-coupling reactions, which is the key

• minimal leaching behaviour is demonstrated with various Suzuki–Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called “plug & play reactor”. Finally, we demonstrate the use of these particles as the sole emulsifier of oil–water emulsions for a range of oils

• , Pd-catalysed C–C cross-coupling reactions have become indispensable in many modern synthetic protocols both in the laboratory and on an industrial scale. A highly important representative of this class of transformation is the Suzuki–Miyaura reaction [5][6], involving the coupling of aryl halides

Synthesis and stability of strongly acidic benzamide derivatives

• Frederik Diness,
• Niels J. Bjerrum and
• Mikael Begtrup

Beilstein J. Org. Chem. 2018, 14, 523–530, doi:10.3762/bjoc.14.38

• , reversed-phase chromatography was chosen to simplify the purifications. The N-triflylbenzamide group also proved stable to cross-coupling reaction conditions, as exemplified by a palladium-catalyzed Suzuki–Miyaura reaction of the 4-bromo-substituted derivative 9d (Scheme 3). The corresponding N,N’-bis

One-pot sequential synthesis of tetrasubstituted thiophenes via sulfur ylide-like intermediates

• Jun Ki Kim,
• Hwan Jung Lim,
• Kyung Chae Jeong and
• Seong Jun Park

Beilstein J. Org. Chem. 2018, 14, 243–252, doi:10.3762/bjoc.14.16

• methods [44][45][46][47][48][49]. In general, Pd-catalyzed Suzuki–Miyaura cross-coupling reactions are the most popular synthetic strategy for aryl–aryl bond-forming reactions [50][51][52]. However, it has been reported that the Suzuki cross-coupling of nitrogen- and sulfur-containing heterocycles is more

Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds

• Baris Temelli and
• Hilal Kalkan

Beilstein J. Org. Chem. 2018, 14, 187–193, doi:10.3762/bjoc.14.13

• -porphyrin, β-corrole-linked hybrid structure described a Suzuki–Miyaura cross-coupling reaction between a β-borylated corrole and meso-bromoporphyrins (Scheme 1D) [37]. Recently, we have successfully synthesized meso–meso and β-meso-linked imine-bridged porphyrin–corrole conjugates and investigated

Fluorescent nucleobase analogues for base–base FRET in nucleic acids: synthesis, photophysics and applications

• Mattias Bood,
• Sangamesh Sarangamath,
• Moa S. Wranne,
• Morten Grøtli and
• L. Marcus Wilhelmsson

Beilstein J. Org. Chem. 2018, 14, 114–129, doi:10.3762/bjoc.14.7

• a more straightforward and versatile synthetic route. The Stille coupling was changed to a Suzuki–Miyaura coupling and the cyclization was performed directly starting from the free aniline nitrogen, as we found that Boc protection was required only for cyclization when using DBU and DABCO. To faster

Structure–property relationships and third-order nonlinearities in diketopyrrolopyrrole based D–π–A–π–D molecules

• Jan Podlesný,
• Lenka Dokládalová,
• Oldřich Pytela,
• Adam Urbanec,
• Milan Klikar,
• Numan Almonasy,
• Tomáš Mikysek,
• Jaroslav Jedryka,
• Iwan V. Kityk and
• Filip Bureš

Beilstein J. Org. Chem. 2017, 13, 2374–2384, doi:10.3762/bjoc.13.235

• 7 using a larger excess of NBS resulted in its decomposition. According to the current literature reports [18][19][27], DPP derivative 8 undergoes smooth cross-coupling reactions. Hence, we have utilized twofold Suzuki–Miyaura and Migita–Stille reactions leading to chromophores 1a–3a and 4a

• , respectively. Commercially available 4-(N,N-dimethylamino)phenylboronic, 4-methoxyphenylboronic, and 2-thienylboronic acids completed with tributyl(5-methoxythiophen-2-yl)stannane, prepared from 2-methoxythiophene [33], were used. Chromophore 4a was also attempted by Suzuki–Miyaura reaction using the

• in modular way prepared by Suzuki–Miyaura, Migita–Stille, and Sonogashira cross-coupling reactions. The chromophores differ in the π-system extension as well as in the peripheral substitution. The thermal stability of 1–5 is mostly affected by the presence of acetylene linkers, 1,4-phenylene and 2,5

Novel approach to hydroxy-group-containing porous organic polymers from bisphenol A

• Tao Wang,
• Yan-Chao Zhao,
• Li-Min Zhang,
• Yi Cui,
• Chang-Shan Zhang and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 2131–2137, doi:10.3762/bjoc.13.211

• organic polymers (POPs) have been reported via Sonogashira–Hagihara coupling reaction [16], Suzuki–Miyaura chemistry [17], Yamato reaction [18], and self condensation of aromatic nitriles[19]. Although these methods can be used to construct POPs with high specific surface area values, these reactions are

Preparation of imidazo[1,2-a]-N-heterocyclic derivatives with gem-difluorinated side chains

• Layal Hariss,
• Kamal Bou Hadir,
• Mirvat El-Masri,
• Thierry Roisnel,
• René Grée and
• Ali Hachem

Beilstein J. Org. Chem. 2017, 13, 2115–2121, doi:10.3762/bjoc.13.208

• as an attractive precursor to increase the molecular diversity around this scaffold. In order to explore this possibility, we performed two Suzuki–Miyaura reactions, as representative examples of Pd-catalyzed coupling processes (Table 3). They gave the target molecules 8 and 9 in 46% and 53% yields

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

• of their low reactivity. Recently, Li and Su with co-workers have developed a liquid-assisted grinding (LAG) method for the Suzuki–Miyaura coupling between aryl chlorides and boronic acids to synthesize the biaryls in nearly quantitative yield. Under optimized conditions 2 mol % Pd(OAc)2 and 4 mol

• ]. Mechanochemical Suzuki reaction [56]. Mechanochemical Suzuki–Miyaura coupling by LAG [57]. Mechanochemical Heck reaction [59]. a) Sonogashira coupling under milling conditions. b) The representative example of a double Sonogashira reaction of p-iodoacetophenone with 1,4-bis-ethynyl benzene. Copper-catalyzed CDC

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

• contributed to Suzuki–Miyaura reactions and only a very few examples were reported for Mizoroki–Heck reactions [45][51][53][57]. Previous research by Rösch and other groups disclosed that introducing a hemilable donor group (such as N, O, S etc.) on the NHC rings was favorable for the palladium-catalyzed

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

• H2PdCl4 in the presence of poly(N-vinylpirrolidone) (PVP) [46][47]. These Pd NPs exhibited highly efficient catalytic activity in Suzuki–Miyaura coupling reactions [46][47] and nitroaromatic hydrogenations [48] in aqueous medium. Outstanding performance of these PVP-Pd NPs in the coupling reaction was

• , precipitation or organic extraction eventually lead to a dramatic drop of the catalytic activity. As a result of this, and in order to perform the reuse experiment, repeated runs on the same batch were performed; reusing the reaction mixture with the PVP-Pd nanocatalyst. By this procedure in both, Suzuki

• –Miyaura coupling reaction [46] and nitroaromatic hydrogenation [48], the PVP-Pd NPs catalytic system exhibited high catalytic activity after five cycles. In the Heck–Mizoroki coupling reaction under MW irradiation, once the reaction was completed, a new batch of reagents was added to the reaction tube and

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Direct catalytic arylation of heteroarenes with meso-bromophenyl-substituted porphyrins

• Alexei N. Kiselev,
• Olga K. Grigorova,
• Alexei D. Averin,
• Sergei A. Syrbu,
• Oskar I. Koifman and
• Irina P. Beletskaya

Beilstein J. Org. Chem. 2017, 13, 1524–1532, doi:10.3762/bjoc.13.152

• ][11], Suzuki–Miyaura [12][13][14][15] and Stille couplings [16][17][18][19][20][21][22] were successfully applied for this purpose. Direct arylation and alkenylation are modern approaches for the formation of C–C bonds, and the application of these methodologies to porphyrins was widely studied by

Development of a method for the synthesis of 2,4,5-trisubstituted oxazoles composed of carboxylic acid, amino acid, and boronic acid

• Kohei Yamada,
• Naoto Kamimura and
• Munetaka Kunishima

Beilstein J. Org. Chem. 2017, 13, 1478–1485, doi:10.3762/bjoc.13.146

• one-pot oxazole synthesis/Suzuki–Miyaura coupling sequence has been developed. One-pot formation of 5-(triazinyloxy)oxazoles using carboxylic acids, amino acids and a dehydrative condensing reagent, DMT-MM, followed by Ni-catalyzed Suzuki–Miyaura coupling with boronic acids provided the corresponding

• 2,4,5-trisubstituted oxazoles in good yields. Keywords: one-pot oxazole synthesis; Suzuki–Miyaura coupling; triazine; 5-(triazinyloxy)oxazole; trisubstituted oxazole; Introduction Oxazoles are found in numerous natural products and are used as a broad range of artificial compounds [1][2]. In

• , Jin and co-workers reported that Ni-catalyzed Suzuki–Miyaura coupling between triazinyloxybenzene and arylboronic acids affords the corresponding biaryl compounds [24][25][26][27][28][29][30][31][32][33]. In this context, we envisioned application of this Suzuki–Miyaura coupling to a 5-(triazinyloxy

Synthesis of the heterocyclic core of the D-series GE2270

• Christophe Berini,
• Thibaut Martin,
• Pierrik Lassalas,
• Francis Marsais,
• Christine Baudequin and
• Christophe Hoarau

Beilstein J. Org. Chem. 2017, 13, 1407–1412, doi:10.3762/bjoc.13.137

• heterocyclic core of the D-series thiopeptide antibiotic GE2270 was prepared. The synthetic strategy that combines direct C–H arylation, Borylation Suzuki–Miyaura cross-coupling (BSC) and Hantzsch thiazole synthesis methods proved to be highly effective regarding the fair 22% yield over 7 synthetic steps from

Nitration of 5,11-dihydroindolo[3,2-b]carbazoles and synthetic applications of their nitro-substituted derivatives

• Roman A. Irgashev,
• Nikita A. Kazin,
• Gennady L. Rusinov and
• Valery N. Charushin

Beilstein J. Org. Chem. 2017, 13, 1396–1406, doi:10.3762/bjoc.13.136

• performed by using the Suzuki–Miyaura cross-coupling reaction with phenylboronic acid under Pd catalysis (Scheme 5). The location of the formyl group and bromine atoms in ICZ derivatives 12 and 13 has been established by X-ray crystallography analysis, performed for single crystals of 12b and 13b (Figure 5

Total synthesis of elansolids B1 and B2

• Liang-Liang Wang and
• Andreas Kirschning

Beilstein J. Org. Chem. 2017, 13, 1280–1287, doi:10.3762/bjoc.13.124

• first synthesis of elansolid B2 (3). The key for improvement was to abandon the two Sonogashira reactions along with the syn-reductions of the two alkynes. Instead, we planned to utilize the Suzuki–Miyaura and the Stille reactions and two Z-configured vinyl iodides to assemble the (Z,E,Z)-triene unit

• . Results and Discussion The improved synthesis utilizes the Suzuki–Miyaura cross-coupling reaction to merge the western fragment derived from ketone 9 with the newly designed eastern building block 13. This fragment was obtained in very good yield from vinyl iodide 12 [9] by a Stille protocol using doubly

• iodide 17 after O-acylation, iodination of the terminal alkyne and finally diimide-mediated syn-reduction [11]. Next, DDQ-mediated removal of the PMB protecting group yielded vinyl iodide 18. The synthesis of both fragments 13 and 18 set the stage for the Suzuki–Miyaura coupling which delivered the

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

• Chinmay A. Shukla and
• Amol A. Kulkarni

Beilstein J. Org. Chem. 2017, 13, 960–987, doi:10.3762/bjoc.13.97

• kinetics parameters of a series-parallel substitution reaction [38]. Reizman et al. have studied Suzuki–Miyaura cross-coupling optimization using a DoE-based algorithm and feedback system [45]. The authors studied both continuous and discrete variables for optimization. Recently Fitzpatrick and Ley have

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