Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• protein conjugate was effectively done with various hydroxylamines with the assistance of the nucleophilic catalyst 5-methoxyanthranilic acid. The resultant histone protein conjugates were functionalized with TAMRA, biotin and the cell-penetrating peptide 'penetratin' through oxime ligation, achieving

Stereoselective mechanochemical synthesis of thiomalonate Michael adducts via iminium catalysis by chiral primary amines

• Michał Błauciak,
• Dominika Andrzejczyk,
• Błażej Dziuk and
• Rafał Kowalczyk

Beilstein J. Org. Chem. 2024, 20, 2313–2322, doi:10.3762/bjoc.20.198

• nucleophilic catalyst. Test reactions between cyclohexenone and thiomalonate 1 conducted in toluene at room temperature indicated the formation of the product with high conversions and efficiencies (Scheme 2). Application of epi-aminoquinine (AQ-1) in combination with 2-fluorobenzoic acid (system A) led to the

An accelerated Rauhut–Currier dimerization enabled the synthesis of (±)-incarvilleatone and anticancer studies

• Tharun K. Kotammagari,
• Sweta Misra,
• Sayantan Paul,
• Sunita Kunte,
• Rajesh G. Gonnade,
• Manas K. Santra and
• Asish K. Bhattacharya

Beilstein J. Org. Chem. 2023, 19, 204–211, doi:10.3762/bjoc.19.19

• accelerate the reaction. In conventional intermolecular RC reactions, the reaction proceeds by the intermolecular addition of a nucleophilic catalyst to the enone substrate to generate an enolate in the first step. In the second step the enolate ion attacks the other Michael acceptor at β-position in an

Synthesis of (Z)-3-[amino(phenyl)methylidene]-1,3-dihydro-2H-indol-2-ones using an Eschenmoser coupling reaction

• Lukáš Marek,
• Lukáš Kolman,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2021, 17, 527–539, doi:10.3762/bjoc.17.47

• . This result is in accordance with the relatively low nucleofugality of diethyl phosphate which is roughly quantified by the pKa = 1.39 of its conjugated acid [43]. We have also examined an addition of 20% of tetrabutylammonium bromide as a nucleophilic catalyst which could transform the phosphate 1g in

Azo-dimethylaminopyridine-functionalized Ni(II)-porphyrin as a photoswitchable nucleophilic catalyst

• Jannis Ludwig,
• Julian Helberg,
• Hendrik Zipse and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2119–2126, doi:10.3762/bjoc.16.179

• activity. The rate constants in the two switching states differ by a factor of 2.2, and the catalytic switching is reversible. Keywords: catalysis; Ni(II)-porphyrins; nucleophilic catalyst; photoswitch; record player molecules; spin switch; Introduction Photoswitchable catalysis has been realized

• . reported on the photoswitching of the basicity of a piperidine nitrogen by reversible steric shielding of the nitrogen lone pair. The photoswitchable base was applied as a nucleophilic catalyst in the nitroaldol (Henry) reaction. Attached to a sterically demanding azobenzene unit, the lone pair was

• study is 4-(N,N-dimethylamino)pyridine derivative 1 (Figure 1). The parent 4-(N,N-dimethylamino)pyridine (DMAP, 2) is known as a nucleophilic catalyst in a number of reactions, for example the Baylis–Hillman reaction [27] and the Steglich esterification [28][29]. To achieve control of the catalytic

Synthesis of oligonucleotides on a soluble support

• Harri Lönnberg

Beilstein J. Org. Chem. 2017, 13, 1368–1387, doi:10.3762/bjoc.13.134

• . When the coupling is carried out at P(V) level, 3´-arylphosphate diesters (3 in Scheme 1) are normally used as building blocks and activated with arylsulfonyl chloride or azolide in the presence of an auxiliary nucleophilic catalyst [14], or a catalytically active phosphate protecting group, such as

• the 4-methoxy-1-oxido-2-picolyl group [15], is used instead of a non-participating arylphosphate group (4 in Scheme 1). Alternatively, prefabricated or in situ activated 1-hydroxybenzotriazole 3´-arylphosphotriesters may be used for coupling in the presence of a nucleophilic catalyst [16][17] (5 in

• pyridine and 2,6-lutidine using 1-(mesitylene-2-sulfonyl)-3-nitro-1,2,4-triazole (MSNT; 6 equiv) as an activator and N-methylimidazole (NMI; 10 equiv) as a nucleophilic catalyst. Each coupling was followed by precipitation/recrystallization from EtOH, capping with Ac2O in pyridine and precipitation from

Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

• Serena Traboni,
• Emiliano Bedini and
• Alfonso Iadonisi

Beilstein J. Org. Chem. 2016, 12, 2748–2756, doi:10.3762/bjoc.12.271

• ][13]. A regioselective silylation of polar saccharide polyols is typically performed with the appropriate silyl chloride in the presence of a high boiling solvent such as DMF or pyridine, often in the presence of a nucleophilic catalyst (more frequently imidazole and DMAP) [14][15][16][17][18][19][20

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

• countless applications [2][3]. The bicylic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, 1, Figure 1) [4], another important Brønsted base in preparative chemistry, may also act as a powerful nucleophilic catalyst [3]. Substituted analogs of TBD [5], such as the chiral compound 2, have become popular

Total synthesis of the proposed structure of astakolactin

• Takayuki Tonoi,
• Keisuke Mameda,
• Moe Fujishiro,
• Yutaka Yoshinaga and
• Isamu Shiina

Beilstein J. Org. Chem. 2014, 10, 2421–2427, doi:10.3762/bjoc.10.252

• already developed the synthetic method of lactones with various ring sizes using 2-methyl-6-nitrobenzoic anhydride (MNBA) under mild reaction conditions in the presence of a nucleophilic catalyst such as 4-(dimethylamino)pyridine (DMAP) [25][26]. By using this method, we have demonstrated that unusual

Concise, stereodivergent and highly stereoselective synthesis of cis- and trans-2-substituted 3-hydroxypiperidines – development of a phosphite-driven cyclodehydration

• Peter H. Huy,
• Julia C. Westphal and
• Ari M. P. Koskinen

Beilstein J. Org. Chem. 2014, 10, 369–383, doi:10.3762/bjoc.10.35

• and 2d (Et3N/DMAP or NMM as bases; Table 1, entries 1 and 2), the protected phenylglycine derivative 2c showed high configurational lability: Under standard conditions (DCC/Et3N/0.3 equiv DMAP) the amide 5c was obtained in a diminished ee of 49% (Table 1, entry 3). HOBt as nucleophilic catalyst proved

• to be even worse than DMAP, because under otherwise identical conditions the product 5c was isolated almost as a racemate (5% ee, entry 4). By replacing Et3N with the less basic NMM (in the presence of DMAP) the ee increased clearly (49→75%, entry 5). However, without any nucleophilic catalyst the

Multivalent display of the antimicrobial peptides BP100 and BP143

• Imma Güell,
• Rafael Ferre,
• Kasper K. Sørensen,
• Esther Badosa,
• Iteng Ng-Choi,
• Emilio Montesinos,
• Eduard Bardají,
• Lidia Feliu,
• Knud J. Jensen and
• Marta Planas

Beilstein J. Org. Chem. 2012, 8, 2106–2117, doi:10.3762/bjoc.8.237

• CH3CN and acetate buffer (0.1 M, pH 4.76) at room temperature for 2 h, but the expected carbopeptide 3 was not obtained. Since the use of aniline as nucleophilic catalyst for oxime ligation has been described to enhance reaction rates by up to three orders of magnitude [31][32][33], we assayed the

Asymmetric desymmetrization of meso-diols by C₂-symmetric chiral 4-pyrrolidinopyridines

• Hartmut Schedel,
• Keizo Kan,
• Yoshihiro Ueda,
• Kenji Mishiro,
• Keisuke Yoshida,
• Takumi Furuta and
• Takeo Kawabata

Beilstein J. Org. Chem. 2012, 8, 1778–1787, doi:10.3762/bjoc.8.203

• pyrrolidinopyridine framework as a catalytic site. Some of these organocatalysts effectively promoted asymmetric desymmetrization of meso-diols via enantioselective acylation. Keywords: acylation; desymmetrization; hydrogen bond; meso-diol; nucleophilic catalyst; organocatalysis; Introduction Since the pioneering

Cyclization of ortho-hydroxycinnamates to coumarins under mild conditions: A nucleophilic organocatalysis approach

• Florian Boeck,
• Max Blazejak,
• Markus R. Anneser and
• Lukas Hintermann

Beilstein J. Org. Chem. 2012, 8, 1630–1636, doi:10.3762/bjoc.8.186

• was not active (Table 1, entry 7), a change to the smaller and more nucleophilic tri-n-butylphosphane, a widely used nucleophilic catalyst [39][40][41][42], produced coumarin in rather high yields. Concentrating on n-Bu3P as a very successful catalyst, a solvent screen was performed at the lower

N-Heterocyclic carbene/Brønsted acid cooperative catalysis as a powerful tool in organic synthesis

• Rob De Vreese and
• Matthias D’hooghe

Beilstein J. Org. Chem. 2012, 8, 398–402, doi:10.3762/bjoc.8.43

• transformed into d3-nucleophiles or homoenolate equivalents 4 through addition of a nucleophilic catalyst across the aldehyde functionality (Scheme 2), a peculiar feature that has been used for the straightforward synthesis of γ-butyrolactones through reaction with aromatic aldehydes [13][14]. In recent years