Enantioselective synthesis of β-aryl-γ-lactam derivatives via Heck–Matsuda desymmetrization of N-protected 2,5-dihydro-1H-pyrroles

• Arnaldo G. de Oliveira Jr.,
• Martí F. Wang,
• Rafaela C. Carmona,
• Danilo M. Lustosa,
• Sergei A. Gorbatov and
• Carlos R. D. Correia

Beilstein J. Org. Chem. 2024, 20, 940–949, doi:10.3762/bjoc.20.84

• complexity in a synthetic route. The palladium-catalyzed coupling of arenediazonium salts with olefins, the Heck–Matsuda reaction, has been instrumental in this strategy involving the desymmetrization of cyclic systems [3], especially five-membered substrates [4][5][6][7]. As we have demonstrated previously

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• -catalyzed reactions. As mentioned above, pyridyl nonaflates derived from the β-ketoenamides KE are excellent substrates for palladium-catalyzed coupling reactions as briefly discussed in our review [23]. Pyrimidyl nonaflates can analogously be used to achieve higher substitution degrees as illustrated by

• with a nonafloxy group all kinds of palladium-catalyzed coupling reactions. Specific oxidation reactions also lead to a variety of new heterocyclic compounds. All the examples collected here show the potential of this approach to highly functionalized heterocycles, furnishing compounds with a very high

• PM50; (NMO = N-methylmorpholine N-oxide). Deprotection of 5-alkoxy-substituted pyrimidines PM2, PM20 and PM29 and conversion into nonaflates PM52 and PM54; (Nf =1-nonafluorobutanesulfonyl). Palladium-catalyzed coupling reactions of PM54 and PM12 giving rise to new pyrimidine derivatives PM55–58

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

• to afford 2 equivalents of the corresponding biphenyl products in nearly quantitative yields (Scheme 34). It is assumed that the first cross coupling reaction with the iodonium salt liberates an aryl iodide moiety, available for the second palladium-catalyzed coupling reaction. Three years later, the

Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones

• Keshaba N. Parida,
• Gulab K. Pathe,
• Shimon Maksymenko and
• Alex M. Szpilman

Beilstein J. Org. Chem. 2018, 14, 992–997, doi:10.3762/bjoc.14.84

• . Recently, Loh reported the palladium-catalyzed coupling of an acid chloride with premade isolable indium homoenolates (In(CH2CHRC=OR')2), 1.2 equiv relative to the acid chloride) to give the corresponding 1,4-diketones [5]. Yet the direct coupling of two enolates is inarguably the shortest and most direct

Total syntheses of the archazolids: an emerging class of novel anticancer drugs

• Stephan Scheeff and
• Dirk Menche

Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108

• suitable olefination strategy. Subsequently, for connecting the resulting fragment to the thiazole subunit 6 a Heck reaction was envisioned as part of studies advancing this type of Palladium-catalyzed coupling strategies in complex target synthesis [61][62][63][64][65][66]. Finally, a HWE-macrocyclization

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

• by quantum chemical DFT/TDDFT calculations carried out for these new molecules. Keywords: bithiophene; donor–acceptor; luminescence; 1,3,4-oxadiazole; palladium-catalyzed coupling; Introduction π-Conjugated donor–acceptor (D-A) compounds are of significant scientific interest because they

• core and the LUMO on the anthracene fragment is observed. Conclusion To summarize, we have shown that ethyl esters of 5'-aryl 3-decyl-2,2'-bithiophene-5-carboxylic acids can be prepared by the palladium-catalyzed coupling of readily available compounds, namely ethyl 3-decyl-2,2'-bithiophene-5

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

• resonances (see Supporting Information File 1). The 1H NMR spectra of porphyrin derivatives 3a–c show the same type of profile; the principal differences are seen in the resonances of the protons and carbon centres of the aryl group inserted by the palladium-catalyzed coupling reaction. As a representative

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

• investigated the synthesis of 4-halogen- and 4,5-bis(halogen)-substituted 6H-1,2-oxazines by halogenation of 6H-1,2-oxazines and subsequent palladium-catalyzed coupling reactions such as Sonogashira or Suzuki–Miyaura reactions [24] leading to aryl- and alkynyl-functionalized products. The synthetic potential

• triflates [46][47] or alkenyl halides [48][49] forming α,β-unsaturated nitriles. As shown in Scheme 7, we adopted a protocol described by Yamamura and Murahashi [48] and found that the palladium-catalyzed coupling of anti-4d with potassium cyanide in the presence of 18-crown-6 at 80 °C in toluene afforded

A T-shape diphosphinoborane palladium(0) complex

• Patrick Steinhoff and
• Michael E. Tauchert

Beilstein J. Org. Chem. 2016, 12, 1573–1576, doi:10.3762/bjoc.12.152

• material (2-bromophenyl)dicyclohexylphosphine (7) was produced by palladium catalyzed coupling of dicyclohexylphosphine with 1-iodo-2-bromobenzene [15]. Phosphine 7 was lithiated in diethyl ether with n-BuLi [16][17], affording the diethyl ether adduct 8. Reaction of 8 with 0.5 equiv of PhBCl2 in toluene

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

• leading to benzannulated medium-sized rings [1][2][3][4] we required starting materials such as alkenyl-substituted compounds B (Scheme 1). Obvious precursors for B are aryl iodides A that smoothly undergo palladium-catalyzed coupling reactions to provide the desired products. However, in one case [A: R1

Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1170–1177, doi:10.3762/bjoc.12.112

• this reaction sequence. For this purpose we prepared other β-ketoenamides, studied their cyclocondensation reactions and used the present functionalities for subsequent reactions, in particular palladium-catalyzed coupling reactions. 2,2´-Bipyridines are a very important class of ligands employed in

• into the corresponding nonafloxy-substituted compounds 5 in good overall yield. These are excellent precursors for palladium-catalyzed coupling reactions as exemplified by the synthesis of compounds such as 9–13. By an attempt to prepare the methoxy-substituted β-ketoenamide 3i by oxidative

Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

• Svetlana P. Panchenko,
• Alexei D. Averin,
• Maksim V. Anokhin,
• Olga A. Maloshitskaya and
• Irina P. Beletskaya

Beilstein J. Org. Chem. 2015, 11, 2297–2305, doi:10.3762/bjoc.11.250

• )-catalysis conditions is a more challenging task than N,N’-diarylation of diamines because copper-catalyzed amination is less selective than palladium-catalyzed coupling. In view of earlier obtained data we used the CuI/L1/EtCN catalytic system for the diarylation of the triamine 5 (Scheme 5, Table 4). In

The simple production of nonsymmetric quaterpyridines through Kröhnke pyridine synthesis

• Isabelle Sasaki,
• Jean-Claude Daran and
• Gérard Commenges

Beilstein J. Org. Chem. 2015, 11, 1781–1785, doi:10.3762/bjoc.11.193

• nonsymmetric quaterpyridines; Constable et al. proposed a multistep synthesis of 4’-(alkylthio)quaterpyridines [23] to avoid the Stille palladium-catalyzed coupling, whereas Fallahpour obtained the 4’-nitroquaterpyridine by employing the Stille coupling method [24]. Sauer et al. extended the use of triazine

C–H-Functionalization logic guides the synthesis of a carbacyclopamine analog

• Sebastian Rabe,
• Johann Moschner,
• Marina Bantzi,
• Philipp Heretsch and
• Athanassios Giannis

Beilstein J. Org. Chem. 2014, 10, 1564–1569, doi:10.3762/bjoc.10.161

• inexpensive dehydroepiandrosterone (5) by the means of a copper-mediated C–H hydroxylation in the 12-position and a palladium-catalyzed coupling of methyl acrylate to an activated enol ether in the 17-position. In synthetic direction (Scheme 2), dehydroepiandrosterone (5) was protected as its

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• preferred over tristannyl derivatives since they are less toxic. However, in recent years the group of Rossi has reported a one-pot procedure for the palladium-catalyzed coupling of aryl iodides 97 with in situ generated Ph2SnBu3 (30, Scheme 27) [170]. When naphthyl triflate was used as a substrate, CuI was

The Flögel-three-component reaction with dicarboxylic acids – an approach to bis(β-alkoxy-β-ketoenamides) for the synthesis of complex pyridine and pyrimidine derivatives

• Mrinal K. Bera,
• Moisés Domínguez,
• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 394–404, doi:10.3762/bjoc.10.37

• methoxyallene 8 with nitriles 9 or 10 and isophthalic acid (11) or diphenic acid (12). Cyclocondensations of β-ketoenamides 13 and 14 to 4-hydroxypyridines 16, 18a and 18b, their subsequent nonaflations and palladium-catalyzed coupling reactions of 19 leading to compounds 21 and 22. NfF = C4F9SO2F

Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

• Andrea Caporale,
• Stefano Tartaggia,
• Andrea Castellin and
• Ottorino De Lucchi

Beilstein J. Org. Chem. 2014, 10, 384–393, doi:10.3762/bjoc.10.36

• extended rection scope that was not included in a previous patent application by our group, in which the decarboxylative coupling reaction for the synthesis of intermediate 2a has been firstly described [76]. Results and Discussion In order to perform efficiently the palladium-catalyzed coupling reaction

• intermediate for the synthesis of Erlotinib hydrochloride (3). Protection of propiolic acid with acetone. Synthesis of 2-methyl-4-(3-aminophenyl)-3-butyn-2-ol-from 3-bomoaniline and 2-methyl-3-butyn-2-ol.a Copper-free palladium-catalyzed coupling of 2-methylbut-3-yn-2-ol (4) with aryl bromides.a Palladium

• -catalyzed coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid and m-bromoaniline.a Palladium catalyzed coupling of 4-hydroxy-4-methyl-2-pentynoic acid (6) with aryl bromides.a Supporting Information Supporting Information File 280: Description of all procedures and characterization data of all new

Synthesis of enones, pyrazolines and pyrrolines with gem-difluoroalkyl side chains

• Assaad Nasr El Dine,
• Ali Khalaf,
• Danielle Grée,
• Olivier Tasseau,
• Fares Fares,
• Nada Jaber,
• Philippe Lesot,
• Ali Hachem and
• René Grée

Beilstein J. Org. Chem. 2013, 9, 1943–1948, doi:10.3762/bjoc.9.230

• representative 5-membered heterocyclic systems with CF2R side chains by using cyclocondensation reactions. Furthermore, selected molecules in these series were functionalized by using appropriate palladium-catalyzed coupling reactions en route to chemical libraries. Results and Discussion The first example of a

Amyloid-β probes: Review of structure–activity and brain-kinetics relationships

• Todd J. Eckroat,
• Abdelrahman S. Mayhoub and
• Sylvie Garneau-Tsodikova

Beilstein J. Org. Chem. 2013, 9, 1012–1044, doi:10.3762/bjoc.9.116

• imidazopyridine, [18F]FPPIP (142), was prepared starting from 140e. A palladium-catalyzed coupling with tributyl(vinyl)tin to give an alkene intermediate was followed by hydroboration-oxidation to give the hydroxypropyl intermediate 145, which was radiolabeled to give 142 (Scheme 10B). This compound showed good

N-Heterocyclic carbene–palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides

• Ismail Özdemir,
• Nevin Gürbüz,
• Nazan Kaloğlu,
• Öznur Doğan,
• Murat Kaloğlu,
• Christian Bruneau and
• Henri Doucet

Beilstein J. Org. Chem. 2013, 9, 303–312, doi:10.3762/bjoc.9.35

• ]. This is especially true for palladium-catalyzed coupling reactions. Pd–NHC catalysts [15] have proven to be excellent alternatives to catalytic systems involving palladium associated to tertiary phosphine ligands [16][17][18][19]. The introduction of aryl groups at C2 or C5 positions of pyrroles is an

• the palladium-catalyzed coupling of heteroarenes with aryl halides through a C–H bond activation has been largely explored. On the other hand, the influence of carbene ligands for such couplings remains largely unexplored [40][41][42][43][44][45][46][47]. Quite congested N-heterocyclic carbene

Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

• Rajendra Surasani,
• Dipak Kalita,
• A. V. Dhanunjaya Rao and
• K. B. Chandrasekhar

Beilstein J. Org. Chem. 2012, 8, 2004–2018, doi:10.3762/bjoc.8.227

• reactions of azaindoles with amides, amines, amino acid esters or phenols offer an interesting complementary method for the synthesis of C–N and C–O bonds under comparably mild conditions. It is important to note that, in contrast to well-established palladium-catalyzed coupling reactions of indole with

Palladium-catalyzed substitution of (coumarinyl)methyl acetates with C-, N-, and S-nucleophiles

• Kalicharan Chattopadhyay,
• Erik Fenster,
• Alexander J. Grenning and
• Jon A. Tunge

Beilstein J. Org. Chem. 2012, 8, 1200–1207, doi:10.3762/bjoc.8.133

• acetate and aryl sulfinate coupling reaction. Scope of the coumarinyl acetate and amine coupling reaction. Reaction development for the coupling of in situ generated enolates and coumarin π-benzyl complexes. Palladium-catalyzed coupling of coumarinyl acetate and phenylboronic acid. Supporting Information

A concise synthesis of 3-(1-alkenyl)isoindolin-1-ones and 5-(1-alkenyl)pyrrol-2-ones by the intermolecular coupling reactions of N-acyliminium ions with unactivated olefins

• Nianhong Lu,
• Lihong Wang,
• Zhanshan Li and
• Wei Zhang

Beilstein J. Org. Chem. 2012, 8, 192–200, doi:10.3762/bjoc.8.21

• -1-one derivatives. One was, as mentioned above, by the Cp2ZrCl2 catalyzed coupling of N-acyliminium ions with in situ generated dimethyl 1-alkenylalanes [24], another was performed by the palladium-catalyzed coupling of 2-iodobenzoyl chloride with aldimines and subsequent cyclization [34]. The

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• indole derivatives have been reported because they occur in numerous natural products and bioactive compounds. Among these different strategies, those involving a palladium-catalyzed coupling reaction have received much attention [25] and one of the most commonly used procedures involves a one-pot two