Gold-catalyzed post-Ugi alkyne hydroarylation for the synthesis of 2-quinolones

• Xiaochen Du,
• Jianjun Huang,
• Anton A. Nechaev,
• Ruwei Yao,
• Jing Gong,
• Erik V. Van der Eycken,
• Olga P. Pereshivko and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2018, 14, 2572–2579, doi:10.3762/bjoc.14.234

• synthesis of 2-quinolones using either intramolecular Heck reaction [60] or Knoevenagel condensation [61][62]. Results and Discussion We began our study with the preparation of the model substrate 7a through the Ugi reaction of tetrolic acid (3a), benzaldehyde (4a), tert-butyl isocyanide (5a) and 3,5

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

• -benzoheptafulvene 178 via reaction paths including the choice of a Michael-type attack of the nucleophile at the C-4 position to Knoevenagel-type attack at the C-1 position [143]. Benzannulated quinotropylidene 180 was produced by the condensation reaction of 2,3-benzotropone (12) and 10H-anthracen-9-one [63]. 2,3

Mannich base-connected syntheses mediated by ortho-quinone methides

• Petra Barta,
• Ferenc Fülöp and
• István Szatmári

Beilstein J. Org. Chem. 2018, 14, 560–575, doi:10.3762/bjoc.14.43

• ortho-amidoalkylation of phenols in which a tandem Knoevenagel condensation occurs through o-QM followed by the formation of an unstable oxazine intermediate [64]. Later, the same research group published a similar reaction extended by various lactams carried out in trifluoroacetic acid in water [65

Curcuminoid–BF₂ complexes: Synthesis, fluorescence and optimization of BF₂ group cleavage

• Henning Weiss,
• Jeannine Reichel,
• Helmar Görls,
• Kilian Rolf Anton Schneider,
• Mathias Micheel,
• Michael Pröhl,
• Michael Gottschaldt,
• Benjamin Dietzek and
• Wolfgang Weigand

Beilstein J. Org. Chem. 2017, 13, 2264–2272, doi:10.3762/bjoc.13.223

• avoid a Knoevenagel condensation at the C-3 atom (Scheme 1a), the β-diketone moiety needs to be fixed into the enol form. In principle, this can be achieved by two different methods. The first one described by Pabon et al. utilises boric oxide in ethyl acetate as an intermediate agent (Scheme 1a) [8

The effect of milling frequency on a mechanochemical organic reaction monitored by in situ Raman spectroscopy

• Patrick A. Julien,
• Ivani Malvestiti and
• Tomislav Friščić

Beilstein J. Org. Chem. 2017, 13, 2160–2168, doi:10.3762/bjoc.13.216

• of reactive encounters between the particles. In contrast, ex situ gas chromatography studies of the Knoevenagel condensation between vanillin and barbituric acid in a planetary mill revealed a sigmoidal dependence of reaction yield with time [22]. Similarly, sigmoidal dynamics were detected by in

• that the reaction progress adopts a sigmoidal profile at milling frequencies higher than 25 Hz, which is consistent with the results of earlier ex situ studies of a Knoevenagel condensation reaction [22]. At milling frequencies below 25 Hz, however, the reaction appears to exhibits linear behavior

Mechanochemical Knoevenagel condensation investigated in situ

• Sebastian Haferkamp,
• Franziska Fischer,
• Werner Kraus and
• Franziska Emmerling

Beilstein J. Org. Chem. 2017, 13, 2010–2014, doi:10.3762/bjoc.13.197

• .13.197 Abstract The mechanochemical Knoevenagel condensation of malononitrile with p-nitrobenzaldehyde was studied in situ using a tandem approach. X-ray diffraction and Raman spectroscopy were combined to yield time-resolved information on the milling process. Under solvent-free conditions, the reaction

• process both result in crystalline products suitable for single crystal X-ray diffraction. Keywords: ball milling; C–C coupling; in situ; Knoevenagel condensation; mechanochemistry; Introduction Mechanochemical syntheses have gained increasing popularity in different areas such as materials science

• interactions such as hydrogen bonds, halogen bonds, and π∙∙∙π interactions [16][17][18][19]. For example, Toda et al. reported yields of 97% for Aldol condensations in the absence of any solvents [20]. Kaupp et al. described the first Knoevenagel condensation in a ball mill [21]. Compared to conventional

Solvent-free sonochemistry: Sonochemical organic synthesis in the absence of a liquid medium

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 1850–1856, doi:10.3762/bjoc.13.179

• that alternative products can be formed using this technique, as with ball milling. The Knoevenagel condensation [18], Michael addition [19] and Biginelli reactions [20] amongst others have been instigated by ultrasonic irradiation in the presence of solvents such as pyridine and methanol, resulting in

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• (62), followed by a Knoevenagel condensation with a variety aromatic aldehydes to give chalcone derivatives 63 (Scheme 21). The reaction of the latter with hydroxylamine hydrochloride, followed by intramolecular 1,4-addition gave 1-indanone derivatives 64a–l which were further tested for in vitro

• -Benzylidene-1-indanones 126a–o were obtained by a Knoevenagel condensation of 1-indanone 125 with various aromatic aldehydes. Hydrogenolysis of 2-benzylidene-1-indanone 126b using Pd/C allowed to obtain 2-benzyl substituted 1-indanone 127 (Scheme 40). 2-Bromo-6-methoxy-3-phenyl-1-indanone 130, as an

• Knoevenagel olefinations, followed by a Nazarov cyclization using FeCl3 or AlCl3. The 2-phosphorylated chalcones (Z)-145 and non-phosphorylated ones (E)-146 could be obtained from the same substrates, β-ketophosphonates 143 and aromatic aldehydes 144 depending on the reaction conditions used (piperidine

Extrusion – back to the future: Using an established technique to reform automated chemical synthesis

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9

• successful by ball milling also. Condensation reactions (e.g., Knoevenagel condensations, Michael additions and Aldol reactions) in particular are the most obvious reaction to be successful by extrusion due to its general success in the ball mill, and as their reactions can be accelerated by the simple

Synthesis of structurally diverse 3,4-dihydropyrimidin-2(1H)-ones via sequential Biginelli and Passerini reactions

• Andreas C. Boukis,
• Baptiste Monney and
• Michael A. R. Meier

Beilstein J. Org. Chem. 2017, 13, 54–62, doi:10.3762/bjoc.13.7

• discussed, is the Knoevenagel type reaction between the aldehyde 1 and β-ketoester 4 followed by a subsequent reaction with urea 2 [20]. The Passerini reaction The Passerini reaction was discovered in 1921 by Mario Passerini and is a three-component reaction between a carboxylic acid 8, a carbonyl compound

Chemical probes for competitive profiling of the quorum sensing signal synthase PqsD of Pseudomonas aeruginosa

• Michaela Prothiwa,
• Dávid Szamosvári,
• Sandra Glasmacher and
• Thomas Böttcher

Beilstein J. Org. Chem. 2016, 12, 2784–2792, doi:10.3762/bjoc.12.277

• synthesized from the chroman-4-one 8 which was produced by base-catalyzed Knoevenagel reaction from 2-hydroxyacetophenone with octanal. Although the starting material was readily available, the reaction gave the product only in low yield (20–30%) and separation of the starting material from the product could

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• cyanoactates in the final synthetic step via Knoevenagel condensation [15][31][32][33][34][35], we chose to begin with (E)-octyl 3-(5-bromothiophen-2-yl)-2-cyanoacrylate as the starting material to ensure good solubility. Intermediate 1 was prepared by palladium-mediated stannylation [36] and then subjected to

Solvent-free, visible-light photocatalytic alcohol oxidations applying an organic photocatalyst

• Martin Obst and
• Burkhard König

Beilstein J. Org. Chem. 2016, 12, 2358–2363, doi:10.3762/bjoc.12.229

• for mechanochemical syntheses include stoichiometric reactions such as the Knoevenagel condensation and the Wittig reaction, but also reactions catalyzed by metal catalysts, like the Sonogashira coupling and the Suzuki coupling [1]. Photocatalysis, as a part of Ostwald’s sub-discipline photochemistry

High performance p-type molecular electron donors for OPV applications via alkylthiophene catenation chromophore extension

• Paul B. Geraghty,
• Calvin Lee,
• Jegadesan Subbiah,
• Wallace W. H. Wong,
• James L. Banal,
• Mohammed A. Jameel,
• Trevor A. Smith and
• David J. Jones

Beilstein J. Org. Chem. 2016, 12, 2298–2314, doi:10.3762/bjoc.12.223

• -dialdehydes 14, Scheme 5, which were purified by a combination of silica chromatography and size exclusion chromatography (SEC). A final Knoevenagel condensation coupling the BXx-dialdehydes with N-hexyl-rhodanine resulted in the required series of products, both BXR and BTxR. The new materials have been

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified

• Knoevenagel condensation of benzyl nitriles and aldehydes produces C–C bonded products with labile nitrile functionalities. In fact, nitrile groups have been shown in porous polymers (particularly in polymers of intrinsic microporosity (PIMs)) to be good precursors to several functionalities like carboxylic

• COP-156 and COP-157, through Knoevenagel nitrile–aldol condensation. COP-156 showed a high surface area (650 m2/g) with a hierarchical porosity, allowing synthetic post-modifications. The nitrile functional groups were first reduced to amine groups (COP-156-amine) and then through reaction with

A chiral analog of the bicyclic guanidine TBD: synthesis, structure and Brønsted base catalysis

• Mariano Goldberg,
• Denis Sartakov,
• Jan W. Bats,
• Michael Bolte and
• Michael W. Göbel

Beilstein J. Org. Chem. 2016, 12, 1870–1876, doi:10.3762/bjoc.12.176

• ][16][17] or from their reduction products, chiral α-amino alcohols [9][18]. In contrast, our approach used the racemic ester rac-12 of β-phenylalanine, easily accessible in a Knoevenagel-type condensation of benzaldehyde 11, ammonium acetate and malonic acid, followed by esterification (Scheme 1) [20

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• (reaction iv), and the final compounds, COOP-nHT-TBDTs 1–4, were obtained by Knoevenagel condensations of CHO-nHT-TBDTs 17–20 with octylcyanoacetate (reaction v). Since all these compounds have multiple alkyl chains, they are soluble in common organic solvents, so that the final compounds can be processed

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

• Franziska Hemmerling and
• Frank Hahn

Beilstein J. Org. Chem. 2016, 12, 1512–1550, doi:10.3762/bjoc.12.148

• units, reductive PKS release and Knoevenagel condensation yield the benzaldehyde intermediate 88. Oxidative dearomatisation of 88 catalysed by the salicylate monooxygenase AteafoD gives 89, which is hydroxylated at C8 by the oxygenase AteafoF. The positioning of this newly formed hydroxy group forces

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• . Some of these post-MCR transformations are: intramolecular cycloaddition reactions, Knoevenagel condensations, metathesis reactions, aza-Wittig reactions, Mitsunobu reactions, etc. [21]. Up to now, two review articles have been reported on azaheterocyclic phosphonates [22][23], but no overview article

• , carbamate 138, hexahydrobenzothiophene 140 and benzothiophene 142 were converted to the corresponding bisphosphonates 139, 141 and 143, respectively (Scheme 30). The synthesized heterocyclic bisphosphonates showed anti-inflammatory properties. 3 Knoevenagel-induced domino reactions An efficient method into

• phosphorylated heterocycles is the condensation of an activated methylene component with a carbonyl compound followed by subsequent transformations such as intramolecular cyclization, Michael-type addition and hetero-Diels–Alder cycloaddition. 3.1 Domino Knoevenagel/phospha-Michael process A convenient one-pot

Creating molecular macrocycles for anion recognition

• Amar H. Flood

Beilstein J. Org. Chem. 2016, 12, 611–627, doi:10.3762/bjoc.12.60

• a difunctional building block for the Knoevenagel condensation that forms cyanostilbenes. Treating the material to carbonate base-catalyzed conditions, he acquired the product in high yields, now optimized to 80% and scaling nicely up to 10 g quantities. The effectiveness of the central binding

(Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers

• Giorgos Koutoulogenis,
• Nikolaos Kaplaneris and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2016, 12, 462–495, doi:10.3762/bjoc.12.48

• ) pathway of a Michael–retro-Michael–Michael–Michael reaction. The same year Zhao and co-workers reported a novel domino Michael–Knoevenagel reaction between 2-mercaptobenzaldehydes 163 and easily accessible Michael acceptors 169 catalyzed by 9-epi-aminoquinine thiourea 57 (Scheme 55) [76]. Various adducts

• good yield and stereoselectivity, given the high molecular complexity that is being achieved in one step (Scheme 64). The researchers suggested that diketone 204 and benzaldehyde 205 reacts through Knoevenagel condensation, to produce 2-arylidene-1,3-indanediones, which is subsequently attacked by the

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• synthesis [65]. This preparation started with a Knoevenagel condensation of 2-fluoroacetophenone with malononitrile. The product of the condensation reacted with an excess of N,N-dimethylformamide dimethyl acetal to afford an enamine. This latter was treated with hydrochloric acid in acetic acid gave 4-aryl

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

• Toxicology (in the 70s). The most recent reviews in this series were published in 2011 [10][11]. Cinnamic acid derivatives can be synthesized using Perkin, Knoevenagel, Claisen [7], and Wittig [12] condensation reactions. Since the discovery of catalytic coupling reactions, cinnamic derivatives have also

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells

• Gleb Sorohhov,
• Chenyi Yi,
• Michael Grätzel,
• Silvio Decurtins and
• Shi-Xia Liu

Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118

• unit. Keywords: donor–acceptor systems; dye-sensitized solar cells; electrochemistry; intramolecular charge transfer; Knoevenagel reaction; tetrathiafulvalene; Introduction Dye-sensitized solar cells (DSSCs) have been intensively investigated as an alternative to silicon-based solar cells [1][2][3][4

• Discussion Synthesis Under Knoevenagel condensation reaction conditions, the corresponding aldehydes 4 and 7 can readily react with cyanoacetic acid leading to the target sensitizers 1 and 2, as depicted in Scheme 1. For the synthesis of the aldehyde precursor 4, the Horner–Wadsworth–Emmons (HWE) reaction

An intramolecular C–N cross-coupling of β-enaminones: a simple and efficient way to precursors of some alkaloids of Galipea officinalis

• Hana Doušová,
• Radim Horák,
• Zdeňka Růžičková and
• Petr Šimůnek

Beilstein J. Org. Chem. 2015, 11, 884–892, doi:10.3762/bjoc.11.99

• Knoevenagel/reduction/hydrolysis/decarboxylation pathway (steps a–d in Scheme 4) to carboxylic acid 10 suffered from low yields of the last two steps (total yield 33%). The attempt to obtain 5a directly from 9 by means of Krapcho decarboxylation [33] failed, as the product was contaminated with inseparable