Asymmetric organocatalytic synthesis of chiral homoallylic amines

• Nikolay S. Kondratyev and
• Andrei V. Malkov

Beilstein J. Org. Chem. 2024, 20, 2349–2377, doi:10.3762/bjoc.20.201

• employing chiral Brønsted acid catalyst (S)-TRIP (118) (Scheme 25). In this approach, the racemic β-formyl amide forms the iminium intermediate that undergoes fast equilibration via the enamine tautomer to form preferentially one enantiomer which then undergoes the acid-catalysed aza-Cope rearrangement

Chiral phosphoric acid-catalyzed transfer hydrogenation of 3,3-difluoro-3H-indoles

• Yumei Wang,
• Guangzhu Wang,
• Yanping Zhu and
• Kaiwu Dong

Beilstein J. Org. Chem. 2024, 20, 205–211, doi:10.3762/bjoc.20.20

• chiral phosphoric acid as a Brønsted acid catalyst and Hantzsch ester as the hydrogen source, a series of 3,3-difluoro-substituted 3H-indoles underwent asymmetric transfer hydrogenation under mild reaction conditions, giving the target products with excellent yields and optical purity. Experimental

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• conjugate Lewis base Brønsted acid catalyst. Sulfenylation of deconjugated butyrolactams. Intramolecular sulfenofunctionalization of alkenes with phenols. Organocatalytic 1,3-difunctionalizations of Morita–Baylis–Hillman carbonates. Organocatalytic sulfenylation of β‑naphthols. Acid-promoted

• acid catalyst I, leading to the formation of an electrophilic sulfenium source (Scheme 49). The use of dimeric cinchona alkaloid J as another organocatalyst for α-sulfenylation of deconjugated butyrolactam substrates 117 with N-(arylsulfanyl)succinimides 1 demonstrated in Mukherjee′s work (Scheme 50

• acid organocatalysts were evaluated for sulfenylation on C3, or C2 position of N-heterocycles 115, including indoles, peptides, pyrrole, and 1-methyl-1H-pyrrolo[2,3-b]pyridine. The authors hypothesized a mechanism for the activation of N-sulfanylsuccinimides 1 or 14 by conjugate Lewis base Brønsted

Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• pyrroles/indoles 4/9 allowing access to 2,3-dihydroisoxazoles 77/78 bearing an all-substituted stereocenter at the C3 position. A dual catalytic activity of the Brønsted acid catalyst was illustrated by the authors which was initiated with a smooth protonation of the OH group in 76 with a subsequnte

• Brønsted acid catalyst to execute a straightforward aza-Friedel–Crafts reaction between 3-substituted indoles 4 and N-sulfonyl-substituted aldimines 128. The reaction successfully installed an aza-tertiary stereocenter at the C2 position of the heterocyclic ring. A broad substrate scope was investigated by

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• Clauson–Kaas reaction in a successive cyclization/annulation process from commercially available sulfonamides 14 in the presence of trifluomethanesulfonic acid (TfOH) as Brønsted-acid catalyst. This procedure produces only N-substituted products and preserves other positions open for further

Supramolecular approaches to mediate chemical reactivity

• Pablo Ballester,
• Qi-Qiang Wang and
• Carmine Gaeta

Beilstein J. Org. Chem. 2022, 18, 1463–1465, doi:10.3762/bjoc.18.152

• capsule can catalyze the cyclization of (S)-citronellal forming isopulegol. In this study it was exploited the ability of the resorcinarene capsule to work as a Brønsted acid catalyst, and its aptitude to stabilize cationic intermediates and transition states inside the cavity. Velmurugan, Hu and co

New advances in asymmetric organocatalysis

• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 240–242, doi:10.3762/bjoc.18.28

• type of Brønsted acid catalyst that expanded the range of available acidities as well as molecular arrangements in acid-catalyzed reactions. Veselý and co-workers demonstrated that these catalysts are effective in the enantioselective aminalization of aldehydes with anthranilamides [24]. To explore new

Transition-metal-free intramolecular Friedel–Crafts reaction by alkene activation: A method for the synthesis of some novel xanthene derivatives

• Tülay Yıldız,
• İrem Baştaş and
• Hatice Başpınar Küçük

Beilstein J. Org. Chem. 2021, 17, 2203–2208, doi:10.3762/bjoc.17.142

• as AlCl3, H2SO4, or H3PO4, which have generally corrosive properties, were used, in this study, an intramolecular ring closure reaction was carried out under easy operating conditions with an organic Brønsted acid catalyst with high yields. So, the xanthene synthesis with alkene activation was

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

• and heterogeneous Brønsted acid catalyst, which are both required for independent steps in the synthesis [132]. They suggested that the porphyrin was protonated by the amberlyst-15 sulphonate groups and immobilised to the solid surface by electrostatic forces, rationalising the observed change in

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

• Svetlana A. Kuznetsova,
• Alexander S. Gak,
• Yulia V. Nelyubina,
• Vladimir A. Larionov,
• Han Li,
• Michael North,
• Vladimir P. Zhereb,
• Alexander F. Smol'yakov,
• Artem O. Dmitrienko,
• Michael G. Medvedev,
• Igor S. Gerasimov,
• Ashot S. Saghyan and
• Yuri N. Belokon

Beilstein J. Org. Chem. 2020, 16, 1124–1134, doi:10.3762/bjoc.16.99

• , providing some dissolved F-1 as the real catalyst. In all cases, the catalyst could easily be recovered and recycled. Keywords: Brønsted acid catalyst; charge-assisted hydrogen-bonded framework; Diels–Alder; epoxide ring opening; heterogeneous catalyst; Introduction Tremendous successes in homogeneous

• Brønsted acid catalyst) cation exchange resin IR-120, which contains sulfonic acid functionalities, was mixed in its hydrogen form with aniline to give a model of F-1. An attempted use of the resulting compound with the same amount of ammonium groups as in F-1 for the conversion of the epoxide 2 into the

• “breathing”. The material served as a new type of Brønsted acid catalyst in a series of reactions, including epoxide ring opening reactions and a Diels–Alder reaction. A second role for NDS was that one of its sulfonate oxygen atoms could form hydrogen bonds with water whilst leaving the other two oxygen

Enantioselective PCCP Brønsted acid-catalyzed aza-Piancatelli rearrangement

• Gabrielle R. Hammersley,
• Meghan F. Nichol,
• Helena C. Steffens,
• Jose M. Delgado,
• Gesine K. Veits and
• Javier Read de Alaniz

Beilstein J. Org. Chem. 2019, 15, 1569–1574, doi:10.3762/bjoc.15.160

• aza-Piancatelli reaction, we sought to identify other asymmetric catalytic systems capable of controlling the absolute stereochemistry. To this end, we envisioned that the chiral pentacarboxycyclopentadiene (PCCP) Brønsted acid catalyst (8) recently developed by the Lambert lab might be suitable

• (Figure 1) [38]. First, the pKa values measured in acetonitrile (MeCN) are lower than chiral phosphoric acids (Brønsted acid pKa = 8.85 vs chiral phosphoric acids pKa = 12–14) [38]. Given the enhanced acidity, we reasoned that this type of chiral Brønsted acid catalyst could facilitate the dehydration

• . Finally, this new catalyst can be produced inexpensively and on scale, features that are attractive for developing a wide range of asymmetric transformations. Results and Discussion Herein, we describe our initial efforts in this area using chiral Brønsted acid catalyst 8. Our investigations began by

cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin

• Dimpee Gogoi,
• Runjun Devi,
• Pallab Pahari,
• Bipul Sarma and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2016, 12, 2816–2822, doi:10.3762/bjoc.12.280

• Friedel–Crafts cyclization (Scheme 2, upper panel) and the products are relevant in the field of natural product-like molecules, because the synthesized molecules are close analogs of a natural product (brazilin). Moreover, the use of TsOH·H2O as an easily-accesible Brønsted acid catalyst with low loading

Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

• Sudipta Pathak,
• Kamalesh Debnath and
• Animesh Pramanik

Beilstein J. Org. Chem. 2013, 9, 2344–2353, doi:10.3762/bjoc.9.269

• Brønsted acid catalyst silica sulfuric acid (SSA). The methodology has a series of intrinsic advantages such as easy preparation of the solid supported SSA from chlorosulfonic acid and silica gel, less energy and manpower usage, easy product isolation/purification and operational simplicity, which lead to

One-step synthesis of pyridines and dihydropyridines in a continuous flow microwave reactor

• Mark C. Bagley,
• Vincenzo Fusillo,
• Robert L. Jenkins,
• M. Caterina Lubinu and
• Christopher Mason

Beilstein J. Org. Chem. 2013, 9, 1957–1968, doi:10.3762/bjoc.9.232

• material. In the Bohlmann–Rahtz reaction, the use of a Brønsted acid catalyst allows Michael addition and cyclodehydration to be carried out in a single step without isolation of intermediates to give the corresponding trisubstituted pyridine as a single regioisomer in good yield. Furthermore, 3

• continuous flow reactor examined the cyclodehydration of Bohlmann–Rahtz aminodienone intermediates in the presence of a Brønsted acid catalyst [44][45]. This relatively simple cyclization reaction was utilized previously as we had already established its facility under microwave irradiation and so it

• = Ph) [51], in the presence of acetic acid as a Brønsted acid catalyst for transfer to flow processing. A range of conditions were investigated (Table 1) and, in each case, 1H NMR spectroscopic analysis of the crude reaction mixture revealed if unreacted starting materials were present. Microwave

Gold(I)-catalysed one-pot synthesis of chromans using allylic alcohols and phenols

• Eloi Coutant,
• Paul C. Young,
• Graeme Barker and
• Ai-Lan Lee

Beilstein J. Org. Chem. 2013, 9, 1797–1806, doi:10.3762/bjoc.9.209

• , entries 8–10). Firstly, no reaction is observed in the absence of a catalyst (Table 1, entry 8). The Brønsted acid catalyst HNTf2 does form chroman 8, but in a poorer isolated yield (21%, Table 1, entry 9) and the silver salt [76] AgNTf2 as a catalyst does not provide any 8, yielding only 9 and 10 (Table

Efficient, highly diastereoselective MS 4 Å-promoted one-pot, three-component synthesis of 2,6-disubstituted-4-tosyloxytetrahydropyrans via Prins cyclization

• Naseem Ahmed and
• Naveen Kumar Konduru

Beilstein J. Org. Chem. 2012, 8, 177–185, doi:10.3762/bjoc.8.19

• and unsymmetrical tetrahydropyrans can be synthesized. p-Toluenesulfonic acid (PTSA) is reported as a versatile Brønsted acid catalyst in various organic transformations [32][33][34]. Previously, PTSA has been used as a catalyst in Prins cyclizations but the product yields were low even under extended

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

• Magnus Rueping and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2010, 6, No. 6, doi:10.3762/bjoc.6.6

• subsequently developed utilizing nanostructured MoO3 (Scheme 11B) [47][48]. Recently, Kobayashi et al. reported a dehydrative nucleophilic substitution of benzyl alcohols in water employing a dodecylbenzenesulfonic acid (DBSA) as a surfactant-type Brønsted acid catalyst. With this green methodology a variety