Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• , their reactivity is higher than that of the corresponding aryl halides, a property that has been widely exploited to develop efficient transition-metal-catalyzed cross coupling reactions [55]. The latter, however, allow for transferring only one of the two aromatic motifs of the iodonium reagents

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

• phosphinoferrocenyl-substituted calixarene ligands 27–29. Asymmetric coupling reaction of aryl boronates and aryl halides in the presence of calixarene mono and di(ferrocenylphosphine) ligands 27 and 28. Asymmetric allylic alkylation in the presence of calix[4]arene ligand (S,S)-29. Asymmetric Tsuji–Trost reaction in

The first Pd-catalyzed Buchwald–Hartwig aminations at C-2 or C-4 in the estrone series

• Ildikó Bacsa,
• Dávid Szemerédi,
• János Wölfling,
• Gyula Schneider,
• Lilla Fekete and
• Erzsébet Mernyák

Beilstein J. Org. Chem. 2018, 14, 998–1003, doi:10.3762/bjoc.14.85

• application of a Pd-catalyzed Buchwald–Hartwig amination. In recent years, extensive efforts have been made on the Pd(0)-catalyzed amination of aryl halides or triflates in order to achieve the efficient synthesis of substituted anilines [6][7][8][9]. Buchwald et al. stated that the Pd source is determining

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

• reagent in the reaction, the substrate 1a was converted to 4a in 27% yield (conditions a), while the dehalogenation was exacerbated in the presence of Pd(OAc)2/PPh3 (conditions b). This phenomenon was in agreement with previous reports [14][15][16], that Pd-catalyzed homocoupling of aryl halides under

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

• unstable [Pd(allyl)Cl]2 intermediate from air. Micelles were also used to perform cross-coupling between benzyl and aryl halides in water [65]. This reaction is known to result in very limited yields due to the undesired homo-coupling reaction between electron-rich and electron-poor benzyl bromides [69

• et al. described a nanogel composed of poly(N-isopropylacrylamide) brushes grafted on Pd-NPs (Pd@PNIPAM) to carry out coupling reactions in water under mild conditions [120]. They showed highly efficient coupling of several hydrophobic aryl halides with phenylboronic acid, which in all cases resulted

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

• , 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

Palladium-catalyzed ortho-halogenations of acetanilides with N-halosuccinimides via direct sp² C–H bond activation in ball mills

• Zi Liu,
• Hui Xu and
• Guan-Wu Wang

Beilstein J. Org. Chem. 2018, 14, 430–435, doi:10.3762/bjoc.14.31

• corresponding N-halosuccinimides. Keywords: acetanilide; ball milling; C–H activation; halogenation; mechanochemistry; N-halosuccinimide; palladium catalysis; Introduction Aryl halides have been widely utilized in organic syntheses, which give access to a range of complex natural products [1][2]. However

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• . Trifluoromethylation of aryl halides using trifluoroacetates as the trifluoromethyl source Reactions employing expensive electrophilic CF3 species such as Umemoto’s reagent or Togni’s reagent, were unpractical and limited on a large-scale synthesis. After comparison of the prices of different CF3 reagents, attention

• . Trifluoromethylation of aryl halides using difluorocarbene precursors as the trifluoromethyl source The trifluoromethyl sources employed in the above-mentioned trifluoromethylations were mainly CF3-containing reagents. Besides, some examples employing difluorocarbene precursors as the trifluoromethylation reagents

• aryl halides in the past years. In contrast, successful examples of copper-catalyzed trifluoromethylation of alkyl halides are quite limited. In 2011, the group of Shibata [25] firstly reported the copper-mediated chemoselective trifluoromethylation at the benzylic position with shelf-stable

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• conditions were not suitable for aliphatic alkynes as they do not undergo oxidative addition with the [NiI] sulfide complex. Miyake and co-workers described a very different approach for the C–S cross-coupling between aryl thiols and aryl halides (Scheme 24) [59]. In a mixture with caesium carbonate as a

Reactivity of bromoselenophenes in palladium-catalyzed direct arylations

• Aymen Skhiri,
• Ridha Ben Salem,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2017, 13, 2862–2868, doi:10.3762/bjoc.13.278

• recent years, the Pd-catalyzed arylation, via a C–H bond activation, of a broad range of heteroaromatics using aryl halides as reaction partners was demonstrated to be particularly effective for the preparation of bi(hetero)aryls [22][23][24][25][26][27][28][29][30][31]. Among the reported results, a few

• examples of Pd-catalyzed direct arylations via the C–H bond activation of selenophenes using aryl halides as coupling partners have been reported [32][33][34][35]. Conversely, C–H bond activation methodology was employed in only in one case for the preparation of a heteroarylated selenophene from a

• , respectively. The use of 2-pentyl- and 2-chlorothiophenes also gave the desired products 10 and 11 in high yields. In general, the Pd-catalyzed direct arylation of 3-substituted thiophenes with aryl halides afforded quite regioselectively the C2-arylated thiophenes [30]. A similar regioselectivity was oberved

Comparative profiling of well-defined copper reagents and precursors for the trifluoromethylation of aryl iodides

• Peter T. Kaplan,
• Jessica A. Lloyd,
• Mason T. Chin and
• David A. Vicic

Beilstein J. Org. Chem. 2017, 13, 2297–2303, doi:10.3762/bjoc.13.225

• bear the trifluoromethyl group have great importance in the life sciences and materials fields as well as discovery chemistry in general [1][2][3]. Consequently, transition-metal-catalyzed methods for preparing aromatic trifluoromethyl compounds from readily available aryl halides are an area that has

• seen rapid growth in the past ten years. Copper is one of the most successfully used metals for mediating the trifluoromethylation of aryl halides, and the active form of the reagents is typically a copper(I) complex bearing a trifluoromethyl ligand, i.e., [LnCu–CF3]. Sporadic examples of

• facilitate meaningful comparative studies, such as structural and electrochemical ones [2]. N-Heterocyclic carbene (NHC) complexes of copper such as A1 (Scheme 1) were the first well-defined and structurally characterized copper–CF3 complexes that display activity for the trifluoromethylation of aryl halides

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

• palladium salts (Pd(OAc)2 or Pd(PPh3)4) and DABCO (1,4-diazabicyclo[2.2.2]octane) various acetylenes and aryl halides were coupled to obtain the Sonogashira coupling products in excellent yields (near quantitative, Scheme 10a). The reactions were reported for aliphatic alkynes as well. In Scheme 10b, an

• significant in organic synthesis because aryl halides are important synthons for the synthesis of many natural and non-natural products [93][94]. In 2005, Rahman and co-workers reported a pioneering solid state benzylic bromination of diquinoline derivatives via N-bromosuccinimide (NBS) [95]. In 2012, Wang

Accessing simply-substituted 4-hydroxytetrahydroisoquinolines via Pomeranz–Fritsch–Bobbitt reaction with non-activated and moderately-activated systems

• Marco Mottinelli,
• Mathew P. Leese and
• Barry V. L. Potter

Beilstein J. Org. Chem. 2017, 13, 1871–1878, doi:10.3762/bjoc.13.182

• aforementioned aims, we envisaged that the synthesis set out in Scheme 2 could deliver access to substrates for the PFB reaction such as 9. After an initial, unfruitful, attempt to obtain the aminoacetals 9 from sequential condensation of aniline and alkyl and aryl halides, a double reductive alkylation that

Ni nanoparticles on RGO as reusable heterogeneous catalyst: effect of Ni particle size and intermediate composite structures in C–S cross-coupling reaction

• Debasish Sengupta,
• Koushik Bhowmik,
• Goutam De and
• Basudeb Basu

Beilstein J. Org. Chem. 2017, 13, 1796–1806, doi:10.3762/bjoc.13.174

• , Jadavpur, Kolkata 700032, India. Fax: +91 33 24730957; Tel: +91 33 23223403 10.3762/bjoc.13.174 Abstract The present work demonstrates the C–S cross-coupling reaction between aryl halides and thiols using nickel nanoparticles (Ni NPs) supported on reduced graphene oxide (Ni/RGO) as a heterogeneous

• formic acid at room temperature [48]. Also, it can serve as an excellent catalyst for the Kumada–Corriu C–C cross-coupling reaction [49]. Since heterogeneous Ni catalysts are rarely studied for the C–S cross-coupling reaction between aryl halides and thiols, presumably because of the fact that the thiols

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

• nanocatalyst. Thus, a variety of aryl halides 1a–h and olefins 2a–c were screened, employing the best reaction conditions above obtained (0.5 mmol of K2CO3, H2O/EtOH, at 130 ºC, Table 2). In all cases, clean and high selective reactions to obtain the trans-products were achieved. By using styrene (2a) and aryl

• perform the coupling reaction between a wide range of aryl bromides and different alkenes. Besides, with demanding substrates like heterocycles, ortho-substituted and non-activated aryl halides, very good results were achieved. Finally, the reusability of PVP-Pd NPs was evaluated in the reaction between 4

• : 10 min; 2º cycle: 20 min; 3º cycle: 30 min, 4º cycle: 30 min, 5º cycle: 30 min. Synthesis of (E)-pterostilbene (19) catalyzed by PVP-Pd NPs. Reaction condition optimizations.a Mizoroki–Heck reaction of aryl halides with olefins catalyzed by PVP-Pd NPs.a Stille–Heck tandem reaction of aryl halides

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

• A. Michael Downey and
• Michal Hocek

Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123

• of the mannosyl donor in three steps and 46% overall yield [64]. 3.4.2 Stereospecific Pd-catalyzed glycosylation: In 2016, Walczak and colleagues [65] described the Pd-catalyzed glycosylation of arenes using anomeric stannanes as donors and aryl halides as the acceptors. The reaction appears to be

• perfectly stereospecific as complete retention of the stereochemistry was observed in all cases. The initial scope used a benzyl-protected glucosylstannane as the donor and a series of aryl halides as acceptors and in all instances the reaction was stereoretentive (Scheme 19) although a mechanistic

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• -catalyzed Ullmann-type coupling reaction has emerged as an effective method, allowing the synthesis of phenols and aryl thiols from aryl halides through C–O and C–S bond formation, respectively [5][6][7]. Very recently, the C–H activation has made revolutionary advances in organic synthesis because it

• methods for the synthesis of these two important classes of compounds. Herein, we review the recent developments on transition-metal-catalyzed syntheses of phenols from aryl halides and arenes, and aryl thiols from aryl halides. Review 1 Transition-metal-catalyzed synthesis of phenols In early times

• , mild reaction conditions, and easy access to starting materials. 1.1 Aryl halide as substrate Compared with other traditional starting materials, such as phenylsulfonic acid, aryl ketone and phenylboronic acid [17][18][19][20], aryl halides can be considered as simple and economical starting materials

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

• react with aryl halides to provide a wide range of products in excellent yields. However, yet there was no evidence of the same technique being applied to steroidal amines. Our particular interest was drawn by the synthesis of cholane-diaminoanthraquinone derivatives that can possess good complexation

Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis

• Flavio Fanelli,
• Giovanna Parisi,
• Leonardo Degennaro and
• Renzo Luisi

Beilstein J. Org. Chem. 2017, 13, 520–542, doi:10.3762/bjoc.13.51

• the process was the use of an integrated supported monolithic Pd(0) catalyst that allowed to perform cross-coupling reactions in continuous flow mode (Scheme 8). This integrated microflow system allow to handle the borylation of aryl halides (Ar1X), and the subsequent Suzuki–Miyaura coupling using

Synthesis and optical properties of new 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles

• Anastasia S. Kostyuchenko,
• Tatyana Yu. Zheleznova,
• Anton J. Stasyuk,
• Aleksandra Kurowska,
• Wojciech Domagala,
• Adam Pron and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2017, 13, 313–322, doi:10.3762/bjoc.13.34

• ) molecules, namely 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2'-bithiophene-5-carboxylate and aryl halides. The obtained compounds feature increasing bathochromic shifts in

• elaboration of a new synthetic procedure. In this communication we present a detailed study of cross-coupling reactions between еthyl 3-decyl-2,2'-bithiophene-5-carboxylate and different aryl halides. The resulting esters are subsequently used as substrates in the preparation of new D–A–D compounds with an

• Discussion Synthetic toolbox It is well known that thiophenes containing acceptor groups such as CHO, CN or CO2Me at the C-2 position readily react with aryl halides in the presence of a Pd(II) catalyst through a Heck-type coupling [26]. We have synthesized the ethyl ester of 2,2'-bithiophene-5-carboxylic

NMR reaction monitoring in flow synthesis

• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31

• catalyst concentration was found. An interesting point to consider is the comparison of in-line and off-line analysis. For example, Duchateau et al. [41] described the preparation of Grignard reagents from aryl halides and magnesium using a fluidized bed reactor under continuous-flow conditions. In a

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• highly efficient neutral organic electron donor (Scheme 25) [127]. This compound is able to reduce aryl halides and appears as the only reductant able to reduce dialkylarenesulfonamides as well as malononitriles without photoexcitation. Electron donor 80 can be isolated but is more conveniently generated

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

• -coupling reaction between N-tosylhydrazones and aryl halides seems to be a powerful method to synthesize new alkene-type derivatives [24][25]. This methodology allowed the development of novel protocols enabling transformations that are difficult to achieve with other reactions and include other important

• the authors reported an efficient methodology for the palladium-catalyzed cross-coupling reaction of electron-deficient aryl halides with aryl N-tosylhydrazones. In such a way, under these new conditions, the reactions between β-bromonated porphyrin 1 and N-tosylhydrazone derivatives 2a–c were

• -catalyzed cross-coupling reaction between aryl halides and N-tosylhydrazones. A retrosynthetic scheme for the synthesis of β-alkenyl-type porphyrin derivatives from the Zn(II) complex of β-bromo-meso-tetraphenylporphyrin and N-tosylhydrazones. Palladium catalysed cross-coupling reactions between β

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

• Pavel Nagorny and
• Zhankui Sun

Beilstein J. Org. Chem. 2016, 12, 2834–2848, doi:10.3762/bjoc.12.283

• during the catalytic process was supported by 13C and 19F NMR studies. Halogen bond donor organocatalysis based on aryl halides The pioneering study of Bolm has attracted significant attention and a number of important studies have emerged since then. In particular, the Huber group has contributed to the

Chromium(II)-catalyzed enantioselective arylation of ketones

• Gang Wang,
• Shutao Sun,
• Ying Mao,
• Zhiyu Xie and
• Lei Liu

Beilstein J. Org. Chem. 2016, 12, 2771–2775, doi:10.3762/bjoc.12.275

• -catalyzed enantioselective addition of aryl halides to both arylaliphatic and aliphatic ketones with high enantioselectivity in an intramolecular version, providing facile access to enantiopure tetrahydronaphthalen-1-ols and 2,3-dihydro-1H-inden-1-ols containing a tertiary alcohol. Keywords: arylation

• -substituted ketone (1i) were also suitable substrate, giving product 2i in 78% ee. The scope of the aryl halide component was next explored (1j–l). Aryl halides bearing different substituent patterns were tolerated giving the tetrahydronaphthalen-1-ols with good ee values. When 4-(2-iodophenyl)butan-2-one (1m