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

• 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

Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides

• Yi Lai,
• Zhijian Zong,
• Yujie Tang,
• Weimin Mo,
• Nan Sun,
• Baoxiang Hu,
• Zhenlu Shen,
• Liqun Jin,
• Wen-hua Sun and
• Xinquan Hu

Beilstein J. Org. Chem. 2017, 13, 213–221, doi:10.3762/bjoc.13.24

• showed a good catalytic efficiency for both Suzuki and Heck cross-coupling reactions. The favorable effect originated from the ring-fused framework being able to establish a strained environment for better stability. Efficient couplings were achieved with aryl bromides or iodides as substrates, however

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

• , affording in such way important intermediates for different synthetic strategies [4][17][18]. There are methods available allowing the insertion of alkenyl groups into porphyrin macrocycles (e.g., Heck reaction [4], metathesis [7][19][20][21], Wittig reaction [22][23]). However, palladium-catalyzed cross

Poly(ethylene glycol)s as grinding additives in the mechanochemical preparation of highly functionalized 3,5-disubstituted hydantoins

• Andrea Mascitti,
• Massimiliano Lupacchini,
• Ruben Guerra,
• Ilya Taydakov,
• Lucia Tonucci,
• Nicola d’Alessandro,
• Frederic Lamaty,
• Jean Martinez and
• Evelina Colacino

Beilstein J. Org. Chem. 2017, 13, 19–25, doi:10.3762/bjoc.13.3

• other alternative energy inputs is still scarce. Only three examples highlight their peculiar role for metal-catalysed processes in a ball mill (Mirozoki–Heck reaction) [6], by ultrasound (copper-catalysed cyanation reaction) [7], and for co-crystal formation in the polymer-assisted grinding process

Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6-dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

• Michal Medvecký,
• Igor Linder,
• Luise Schefzig,
• Hans-Ulrich Reissig and
• Reinhold Zimmer

Beilstein J. Org. Chem. 2016, 12, 2898–2905, doi:10.3762/bjoc.12.289

• -forming reactions such as Sonogashira, Heck, or Suzuki coupling reactions as well as a cyanation reaction. These cross-coupling reactions led to a series of 5-alkynyl-, 5-alkenyl-, 5-aryl- and 5-cyano-substituted 1,2-oxazine derivatives being of considerable interest for further synthetic elaborations

• -oxazine syn-11 in 41% yield. Next, we briefly studied 5-iodo-1,2-oxazine syn-4a as substrate in Heck reactions. The substrate was reacted with the alkyl acrylates 12a (R1 = Me) and 12b (R1 = t-Bu) under phosphine-free conditions [33][34] using 6 mol % of palladium(II) acetate, triethylamine as base and

• lithium chloride [35] leading to the expected coupling products syn-13 and syn-14 in 39% and 82% yield, respectively (Scheme 5). In both cases, only the E-configured 2-substituted alkyl acrylates were isolated. The moderate yield in the Heck reaction with methyl acrylate 12a is very likely caused by the

Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I)

• Sem Raj Tamang and
• James D. Hoefelmeyer

Beilstein J. Org. Chem. 2016, 12, 2757–2762, doi:10.3762/bjoc.12.272

• ]. Recently, we reported the Pd(II) complex catalyzed Heck-type C–C coupling [51]. The observation may implicate reductive elimination and oxidative addition can cycle repeatedly on the palladium center coordinated to 1. With this in mind, we sought to utilize the Cu(I) complex, chloro[8-(dimesitylboryl

Rapid regio- and multi-coupling reactivity of 2,3-dibromobenzofurans with atom-economic triarylbismuths under palladium catalysis

• Maddali L. N. Rao,
• Jalindar B. Talode and
• Venneti N. Murty

Beilstein J. Org. Chem. 2016, 12, 2065–2076, doi:10.3762/bjoc.12.195

• the synthesis of 2,3-dialkenylbenzofurans and functionalized dibenzofurans with domino “twofold Heck/6π-electrocyclization” of 2,3-di- and 2,3,5-tribromobenzofuran substrates [34]. In this regard, the cross-coupling studies of triarylbismuth reagents in regioselective studies with functionalized

Scope and limitations of a DMF bio-alternative within Sonogashira cross-coupling and Cacchi-type annulation

• Kirsty L. Wilson,
• Alan R. Kennedy,
• Jane Murray,
• Ben Greatrex,
• Craig Jamieson and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2016, 12, 2005–2011, doi:10.3762/bjoc.12.187

• ][35], Mizoroki–Heck [36][37], Sonogashira [38], Stille [39], Hiyama reactions [40], and hydroformylation reactions [41]. In the current study, we present the use of Cyrene as an alternative solvent (direct DMF replacement) for the Sonogashira reaction, as well as related Cacchi-type annulations [42

• -used organic transformations. For example, the majority of many other standard cross-coupling processes employ inorganic or organic bases and heat (e.g., Suzuki–Miyaura, Heck). Accordingly, Cyrene may be projected to be incompatible with standard conditions for these reactions and its use would

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

• Jakub Saadi,
• Christoph Bentz,
• Kai Redies,
• Dieter Lentz,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1236–1242, doi:10.3762/bjoc.12.118

• –R2 = (CH2)4] typical Heck reaction conditions employing styrene as olefin component not only led to the desired styrene derivative B but mainly to the cyclized product C. If the reaction was performed without the olefin it provided only the tertiary alcohol C in reasonable yield [5]. Similar C–C bond

• structure (ORTEP, [14]) of compound 14a (thermal ellipsoids at 50% probability). Molecular structure (ORTEP, [14]) of compound 15a (thermal ellipsoids at 50% probability). Molecular structure (ORTEP [14]) of compound 15b (thermal ellipsoids at 50% probability). Planned Heck reaction of A to compound B and

Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

• Takashi Nishikata,
• Alexander R. Abela,
• Shenlin Huang and
• Bruce H. Lipshutz

Beilstein J. Org. Chem. 2016, 12, 1040–1064, doi:10.3762/bjoc.12.99

• generally resorted to elevated temperatures (80–160 °C) and anhydrous conditions, and in many cases high pressures of CO or O2 are also required in order to carry out these Heck-like coupling reactions [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][193][194][195][196][197

• results in the formation of a monocationic arylpalladium(II) palladacycle, likely via a Wheland-like intermediate (Scheme 23) [233][234][235][236][237]. The product-forming portion of the cycle may proceed in a manner resembling a traditional Heck cross-coupling. In this case, addition of the palladacycle

• to an acrylate followed by β-hydride elimination yields the corresponding product 5. As previously demonstrated in palladium-catalyzed Mizoroki–Heck reactions [238][239][240], insertion of a alkenyl double bond into C–Pd+ present within the cationic palladacyle is facile, owing to the high Lewis

Enantioselective carbenoid insertion into C(sp³)–H bonds

• J. V. Santiago and
• A. H. L. Machado

Beilstein J. Org. Chem. 2016, 12, 882–902, doi:10.3762/bjoc.12.87

• activation; chiral catalysis; diazo compounds; total synthesis; Introduction One of the major challenges met in organic synthesis is the formation of carbon–carbon bonds, in particular in a stereoselective way. Nucleophilic substitution reactions, radical reactions, cross-coupling reactions and the Heck

A modular approach to neutral P,N-ligands: synthesis and coordination chemistry

• Vladislav Vasilenko,
• Torsten Roth,
• Clemens K. Blasius,
• Sebastian N. Intorp,
• Hubert Wadepohl and
• Lutz H. Gade

Beilstein J. Org. Chem. 2016, 12, 846–853, doi:10.3762/bjoc.12.83

• hydrogenations [1][2] and allylic substitutions [3][4] to Heck reactions [5] and conjugate additions to enones [6]. Their popularity arises from the inherent electronic disparity of the phosphorus and the nitrogen donor groups, rendering one binding site a soft π-acceptor featuring a pronounced trans effect and

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

Study on the synthesis of the cyclopenta[f]indole core of raputindole A

• Nils Marsch,
• Mario Kock and
• Thomas Lindel

Beilstein J. Org. Chem. 2016, 12, 334–342, doi:10.3762/bjoc.12.36

• , which was synthesized via Heck reaction with but-3-en-2-ol (5, 89%) in the presence of LiCl, inspired by a procedure by Camp and coworkers [36]. Propargyl bisindole 7 was obtained after conversion of 4 (2 equiv) to the magnesium acetylide (iPrMgCl in THF) and Grignard reaction with ketone 6. Due to the

• ketone 26 proceeded in the highest yield of all our Meyer–Schuster rearrangements. With triflated α,β-unsaturated ketone 26 in hand, we attempted reductive Heck cyclizations to the raputindole core structure. For instance, we employed Pd(dba)2 (12 mol %), QPhos (24 mol %), and NEt3 (1.20 equiv) in DMF at

Hydroquinone–pyrrole dyads with varied linkers

• Hao Huang,
• Christoffer Karlsson,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 89–96, doi:10.3762/bjoc.12.10

• derivatives and pyrrolylboronic acids should be possible. Ethylene linker: Synthesis of 3-(2,5-dimethoxystyryl)-1H-pyrrole (3c) Our initial approach of synthesizing vinyl linker dyad 3c was to use a Heck reaction, coupling 3-iodo-1-(triisopropylsilyl)-1H-pyrrole and dimethoxystyrene. A variation of reaction

• , see Supporting Information File 2). According to a study by Liu et al. [19], the protecting group for 3-iodo pyrrole is essential in the Heck reaction involving pyrrole. Based on this suggestion, 3-iodo-1-tosyl-1H-pyrrole was also tested but did not result in any product. It is worth to mention that

N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions

• Senem Akkoç,
• Yetkin Gök,
• İlhan Özer İlhan and
• Veysel Kayser

Beilstein J. Org. Chem. 2016, 12, 81–88, doi:10.3762/bjoc.12.9

• complexes have been used in different coupling reactions such as Mizoroki–Heck cross-coupling [22][23], Suzuki–Miyaura cross-coupling [24][25], Sonogashira [26] and arylation reactions [27]. There are suitable precatalyst scaffolds, which were developed by Nolan [28], Organ [21] and Buchwald [29]. To find

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

• Kirk W. Shimkin and
• Donald A. Watson

Beilstein J. Org. Chem. 2015, 11, 2278–2288, doi:10.3762/bjoc.11.248

• , internal alkenes (such as 39) were not affected during the reaction. Although the reaction proceeds via a distinct mechanism, the authors refer to the transformation as a formal Heck-type alkenylation of alkyl bromides. As with the nitroalkane alkylation chemistry illustrated above, this reaction is a rare

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

• -configuration were formed by SmI2-mediated reductive dimerization of a 4-(indol-6-yl)butenone, obtained by Heck reaction. The two indolyl units appear to chelate Sm(II)/(III) leading to a gauche-type arrangement at the newly formed bond between the two β-carbons. Through a sequence of Sonogashira cross coupling

• the crude material, 6-iodoindole was purified conveniently by sublimation in high vacuum affording a colorless product. The natural product (E)-4-(1H-indol-6-yl)but-3-en-2-one (5) isolated from Monodora angolensis [12] was obtained from 6-iodoindole (4) in one step via Heck reaction with methyl vinyl

• aliphatic side chain was introduced via N-isovaleroylpiperidine [36]. Removal of the TBS group by treatment with TBAF gave the natural product 20 in 47% yield as a colorless solid. Synthesis and biological activity of indiacen B The successful Heck reaction at unprotected 6-iodoindole prompted us to check

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• -coupling reactions with varied degree of success. The most efficient cross-coupling reactions were the Heck reactions with alkenes, a biaryl homocoupling reaction, an azo coupling to electron-rich arenes, and a dediazoniation with TMSN3 in an ionic liquid medium [74][75]. An efficient borylation of

Pd(OAc)₂-catalyzed dehydrogenative C–H activation: An expedient synthesis of uracil-annulated β-carbolinones

• Biplab Mondal,
• Somjit Hazra,
• Tarun K. Panda and
• Brindaban Roy

Beilstein J. Org. Chem. 2015, 11, 1360–1366, doi:10.3762/bjoc.11.146

• -carbolinones have been developed [32][33][34][35][36], such as an intramolecular Heck reaction strategy of 2- and 3-iodoindoles for the synthesis of β- or γ-carbolinones by Beccalli et al. [32], AuCl3 and Pd-catalyzed cycloisomerization of indole-2-carboxamides to β-carbolinones [33][34][35], Pd-catalyzed

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• Heck coupling: In 2003, Snieckus and co-workers [97] have synthesized the seco-C/D ring analogues of ergot alkaloids through the intramolecular Heck reaction as a key step. The coupling precursors 63 and 68 were prepared from 4-bromoindoles by a sequential Vilsmeier–Haack, Henry nitroaldol condensation

Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

• Jerzy Zakrzewski and
• Bogumiła Huras

Beilstein J. Org. Chem. 2015, 11, 1155–1162, doi:10.3762/bjoc.11.130

• Mizoroki–Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. Keywords: 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1

• -oxyl; cinnamates; Mizoroki–Heck cross-coupling reaction; nitroxides; Introduction Cinnamic acid derivatives are known as biologically active compounds. Cinnamic acid and its hydroxy derivatives bearing a phenolic moiety such as coumaric, caffeic, ferulic, sinapinic, and chlorogenic acids [2][3][4][5

• been obtained using the Mizoroki–Heck cross-coupling reaction between aryl halides and an olefin [7][13][14][15][16][17]. Because cinnamates themselves are also olefins, they can serve as cinnamic substrates to synthesize more complex cinnamates [18][19]. Cinnamic acid derivatives are also formed when

Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

• Antonio Monopoli,
• Pietro Cotugno,
• Carlo G. Zambonin,
• Francesco Ciminale and
• Angelo Nacci

Beilstein J. Org. Chem. 2015, 11, 994–999, doi:10.3762/bjoc.11.111

• allylic alkylation of nucleophiles [30][31][32][33][34][35][36]. Some years ago, we synthesized the first example of Pd–benzothiazol-2-ylidene complex I (Figure 1), which proved to be an efficient catalyst for several C–C coupling reactions (like carbonylations and Heck olefinations) carried out in both

Matsuda–Heck reaction with arenediazonium tosylates in water

• Ksenia V. Kutonova,
• Marina E. Trusova,
• Andrey V. Stankevich,
• Pavel S. Postnikov and
• Victor D. Filimonov

Beilstein J. Org. Chem. 2015, 11, 358–362, doi:10.3762/bjoc.11.41

• Chemistry of New Materials NAS Belarus, 220141, Minsk, Belarus Department of General and Inorganic Chemistry, National Research Tomsk Polytechnic University, 634050 Tomsk, Russia 10.3762/bjoc.11.41 Abstract An environmentally friendly Matsuda–Heck reaction with arenediazonium tosylates has been developed

• ; diazonium salts; Matsuda–Heck reaction; microwave-assisted synthesis; stilbenes; Introduction Diazonium salts are known as one of the most valuable building blocks in organic synthesis [1]. Today, their most common use is the construction of carbon–carbon bonds in palladium-catalyzed reactions. Starting

• with the work of Matsuda’s group [2], who used a diazonium salt as a high-reactive electrophile for a Heck reaction, the Matsuda–Heck reaction does require the addition of neither bases nor ligands and is carried out under very mild conditions [3]. Furthermore, diazonium salts are more often prepared

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• -catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high

• study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. Keywords: asymmetric hydroformylation; cyclodextrin; Heck reaction; homogeneous catalysis; palladium; phosphine; rhodium; Introduction Since the studies of Fu

• , Buchwald and Hartwig on the use of monophosphine ligands in cross-coupling reactions, notably carbon–carbon ones such as the Mizoroki–Heck [1][2][3] and Suzuki–Miyaura reactions [4][5][6], there is a renewed interest for tertiary phosphines that favour the formation of singly phosphorus-ligated complexes