Salen–scandium(III) complex-catalyzed asymmetric (3 + 2) annulation of aziridines and aldehydes

• Linqiang Wang and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1087–1094, doi:10.3762/bjoc.21.86

• derivatives were obtained under asymmetric catalysis with a Ni(II)–bisoxazoline complex [15] and a Nd(OTf)3/N,N'-dioxide/LiNTf2 delay catalytic system [16], respectively (Scheme 1b and c). However, further exploration for convenient asymmetric catalytic synthetic methods is still in demand because the former

New advances in asymmetric organocatalysis II

• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 766–769, doi:10.3762/bjoc.21.60

• already been described by Seebach et al. in 1982 [15]. From this perspective, organocatalysis is more than 100 years old, building on a long thread of illustrious past discoveries. Asymmetric organocatalysis is now considered one of the three main pillars of asymmetric catalysis, along with metal

Asymmetric synthesis of β-amino cyanoesters with contiguous tetrasubstituted carbon centers by halogen-bonding catalysis with chiral halonium salt

• Yasushi Yoshida,
• Maho Aono,
• Takashi Mino and
• Masami Sakamoto

Beilstein J. Org. Chem. 2025, 21, 547–555, doi:10.3762/bjoc.21.43

• corresponding products in excellent yields with up to 86% ee. To the best of our knowledge, the present paper is the first to report the asymmetric construction of β-amino cyanoesters with contiguous tetrasubstituted carbon stereogenic centers by the catalytic Mannich reaction. Keywords: asymmetric catalysis

• organic chemistry [2][3][4][5], organocatalysis [6][7], metal catalysis [8][9], biochemistry [10][11], materials science [12][13], and supramolecular chemistry [14][15], although its successful application to asymmetric catalysis has been limited (Figure 1) [16][17][18][19][20]. In 2018, Arai and co

• ]. Hypervalent halogen compounds have been utilized as highly reactive substrates [21][22][23][24][25][26][27] and have recently been reported to work as halogen-bonding catalysts [28][29][30][31]. Previously, chiral halonium salts have been utilized in asymmetric catalysis [32][33][34][35], and we have

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• becoming increasingly relevant also in medicine. Many axially chiral compounds are important as catalysts in asymmetric catalysis or have chiroptical properties. This review overviews recent progress in the synthesis of axially chiral compounds via asymmetric organocatalysis. Atroposelective

• compounds comprising a stereogenic plane or axis is much less developed. Axially chiral compounds are well known as chiral ligands in asymmetric catalysis, with notable examples of binaphthyl-based derivatives such as BINAP, SEGPHOS, or binaphthyl-based phosphoric acid derivatives, which are among the

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N,N’-dioxide

• Noble Brako,
• Sreerag Moorkkannur Narayanan,
• Amber Burns,
• Layla Auter,
• Valentino Cesiliano,
• Rajeev Prabhakar and
• Norito Takenaka

Beilstein J. Org. Chem. 2024, 20, 3069–3076, doi:10.3762/bjoc.20.255

• benzaldehydes, which may be attributable to that they have smaller steric demands in the vicinity of the carbonyl carbon atom than benzaldehyde. Importantly, we did not observe the corresponding homopropargylic alcohols [51] in all cases. Since this work is the first asymmetric catalysis study of isomerically

Computational design for enantioselective CO₂ capture: asymmetric frustrated Lewis pairs in epoxide transformations

• Maxime Ferrer,
• Iñigo Iribarren,
• Tim Renningholtz,
• Ibon Alkorta and
• Cristina Trujillo

Beilstein J. Org. Chem. 2024, 20, 2668–2681, doi:10.3762/bjoc.20.224

• catalyst efficiency and selectivity in sustainable chemistry applications. Keywords: asymmetric catalysis; carbon dioxide; CO2; epoxide; frustrated Lewis pairs (FLPs); volcano plot; Introduction The field of frustrated Lewis pairs (FLPs) has flourished since their seminal discovery in 2006 by Stephan and

• conditions [37][38][39]. When considering asymmetry, it was necessary to include large substituents on the catalyst to induce steric hindrance. These modifications increase the size of the asymmetric catalysts. Thus, the calculations presented in subsection “Asymmetric catalysis” were optimised at the B3LYP

• boron bears CF3 substituents. Thus, an acidic boron atom seems to increase the reactivity of the considered system. Concerning the LB, it appears that, as opposed to the first group of compounds, a phosphorus atom is more active than a nitrogen atom. Asymmetric catalysis After examining the volcano

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

• , encompassing cutting-edge advances in hydrogen-bond catalysis and non-classical approaches. Furthermore, practical examples showcasing the application of these innovative methodologies in total synthesis are presented. Keywords: asymmetric catalysis; asymmetric synthesis; chiral amines; organicatalysis

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

• nucleophiles in this transformation. Keywords: asymmetric catalysis; iminium catalysis; mechanochemistry; organocatalysis; thioesters; Introduction Mechanochemistry, particularly solventless processes under ball milling conditions, offers the opportunity to devise unconventional reaction pathways [1][2][3][4

• = Ph). Finally, an interesting group of β-ketothioesters 5–8, which are rarely utilized in asymmetric catalysis [45], were employed as nucleophiles in reactions with acceptor E1 (Scheme 7). While additions of various β-ketothioesters, including 5–8, to nitrostyrenes proceeded efficiently, leading to

Chiral bifunctional sulfide-catalyzed enantioselective bromolactonizations of α- and β-substituted 5-hexenoic acids

• Sao Sumida,
• Ken Okuno,
• Taiki Mori,
• Yasuaki Furuya and
• Seiji Shirakawa

Beilstein J. Org. Chem. 2024, 20, 1794–1799, doi:10.3762/bjoc.20.158

• without substituents on the carbon–carbon double bond have remained a formidable challenge. To address this limitation, we report herein the asymmetric bromolactonization of 5-hexenoic acid derivatives catalyzed by a BINOL-derived chiral bifunctional sulfide. Keywords: asymmetric catalysis

A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-b]oxazol-6-ium salts

• Andrew D. Gillie,
• Matthew G. Wakeling,
• Bethan L. Greene,
• Louise Male and
• Paul W. Davies

Beilstein J. Org. Chem. 2024, 20, 621–627, doi:10.3762/bjoc.20.54

• secondary gold-ligand interactions [8][9][10], chiral environments [11][12][13] including those enabling secondary interactions with substrates for asymmetric catalysis [14], cooperative and bimetallic catalysis [7][15], and redox-enabling function for Au(I)/(III) cycles [16][17]. Such L-shaped ligands

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• of alkenes remains challenging. Advances in asymmetric catalysis [2][3][4][5][6][7][8][9][10], C–N [11][12][13][14][15][16][17] and C–C functionalization [18][19] reveal opportunities, but harsh conditions and limited substrate scope present problems. Intramolecular reactions almost invariably

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• ] are deprotonated, and tautomers I and II add to an enolate acceptor. For anion–π catalysis, nitroolefins like 5 [60] were convenient acceptors because they are compatible with asymmetric catalysis, and because stabilization of intermediate III by privileged nitronate-π interactions drives the reaction

• surface of carbon allotropes can increase diastereo- and enantioselectivity of Diels–Alder reactions. The direct formation of 1,3-nonadjacent stereocenters is a topic of concern in asymmetric catalysis [67]. To explore compatibility with anion–π catalysis, the addition of ethyl 2-cyano-2-phenylacetate (28

• respective electron-poor motifs by induced cation–π interactions, and the combination with co-catalysts interfaced on MWCNTs should provide general access to asymmetric catalysis. OEEF-induced anion–π and cation–π catalysis on carbon allotropes, affordable, clean and general, thus have the potential to non

Asymmetric tandem conjugate addition and reaction with carbocations on acylimidazole Michael acceptors

• Brigita Mudráková,
• Renata Marcia de Figueiredo,
• Jean-Marc Campagne and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 881–888, doi:10.3762/bjoc.19.65

• obtained by other conjugate addition reactions. Keywords: acylimidazole; asymmetric catalysis; carbocation; conjugate addition; enolate; Introduction Asymmetric metal-catalyzed conjugate additions provide access to numerous chiral scaffolds. This type of C–C bond formation efficiently enables the

• its applications in the total syntheses of complex natural products and other molecules of biological relevance [13][14]. Acylimidazoles proved to be versatile building blocks broadly applicable in asymmetric catalysis and organic synthesis. Today, acylimidazoles are used as ester/amide surrogates

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• products. Keywords: amino acids; asymmetric catalysis; multicomponent reaction; palladium catalysis; Petasis reaction; sulfonamides; Introduction α-Amino acids play a crucial role in every aspect of our human life [1]. They are important synthetic intermediates in the chemical industry and used for the

Synthesis of medium and large phostams, phostones, and phostines

• Jiaxi Xu

Beilstein J. Org. Chem. 2023, 19, 687–699, doi:10.3762/bjoc.19.50

• the catalytic antibody [24]. They are also potential chiral ligands in asymmetric catalysis [25] (Figure 1). Cyclizations and annulations are two major strategies for the synthesis of medium and large phostam, phostone, and phostine derivatives. The cyclizations have been applied in the construction

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• . Short information on applications in total synthesis is also given. Keywords: asymmetric catalysis; conjugate addition; electrophile; enolate; tandem reaction; Introduction The formation of complex chiral molecules is a crucial task of organic synthesis that enables the synthesis of pharmaceuticals

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• organic chemistry. It allows chemists to avoid the use of precious and (or) toxic metals by taking advantage of the catalytic activity of small and synthetically available molecules. Today, the term organocatalysis is mainly associated with redox-neutral asymmetric catalysis of C–C bond-forming processes

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

• the synthesis and properties of such BINOL-based chiral MIMs, together with their use in further diastereoselective modifications, their application in asymmetric catalysis, and stereoselective chemosensing. In their minireview, Prodip Howlader and Michael Schmittel [22] highlighted the recent results

Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes

• Almaz A. Zagidullin,
• Farida F. Akhmatkhanova,
• Mikhail N. Khrizanforov,
• Robert R. Fayzullin,
• Tatiana P. Gerasimova,
• Ilya A. Bezkishko and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1338–1345, doi:10.3762/bjoc.18.139

• objects of growing interest in the fields of coordination chemistry [3][4][5] and asymmetric catalysis [6][7]. Due to the sp2-hybridization of the phosphorus atom, phosphaferrocenes are commonly regarded as phosphorus ligands with weaker σ-donor character than classical tertiary phosphines and stronger π

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• catalysts has been successfully developed employing dynamic metal–ligand coordination bonds. While only a small fraction of these 3D architectures was useful for chiral catalysis, an even smaller fraction was able to provide a high stereoselectivity during asymmetric catalysis [5]. For instance, an

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• '-binaphthyl-2,2'-diol (BINOL) unit as a stereogenic element in mechanically interlocked molecules (MIMs). We describe the synthesis and properties of such BINOL-based chiral MIMs, together with their use in further diastereoselective modifications, their application in asymmetric catalysis, and their use in

• chemosensing or in asymmetric catalysis. The selection of suitable stereogenic elements is of great importance [26][27][28]. The most straightforward way to create a chiral rotaxane or catenane is the introduction of classical chiral elements, such molecular parts with axial chirality, point chirality, or

• described in chapter 1, the mechanical bond allows a chirality transfer from a chiral, BINOL-based macrocycle to an achiral thread. Thus, it is conceivable that placing a catalytically active group onto the thread would allow for asymmetric catalysis based on chirality transfer from a BINOL macrocycle. In

Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions

• Hao Guo,
• Yu-Fei Ao,
• De-Xian Wang and
• Qi-Qiang Wang

Beilstein J. Org. Chem. 2022, 18, 486–496, doi:10.3762/bjoc.18.51

• tertiary amine sites were found to be crucial for achieving efficient activation and stereocontrol. As shown in control experiments, catalysis with the acyclic analogues having the same structural motifs were non-selective. Keywords: chiral macrocycles; cooperative asymmetric catalysis; decarboxylative

Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water

• Zhihang Bai,
• Krishnasamy Velmurugan,
• Xueqi Tian,
• Minzan Zuo,
• Kaiya Wang and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2022, 18, 429–437, doi:10.3762/bjoc.18.45

• a photocatalytic dehalogenation reaction, i.e., debromination of 2-bromo-1-phenylethanone derivatives with high yields and short reaction time in an aqueous solution. Based on the above results, the fabricated AIE-emissive FRET system with chiral guest can be further utilized for asymmetric

• catalysis in water, which is currently underway in our laboratory. 1H NMR (400 MHz, D2O, 298 K) spectra of m-TPEWP5 (1.0 mM), m-TPEWP5 (1.0 mM) + G (1.0 mM), and G (1.0 mM). (a) Fluorescence spectra of m-TPEWP5 (1 × 10−5 M) with different concentrations of G (0 to 1.2 equiv); (b) Job’s plot of m-TPEWP5G

New advances in asymmetric organocatalysis

• Radovan Šebesta

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

• Radovan Sebesta Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia 10.3762/bjoc.18.28 Keywords: asymmetric organocatalysis; covalent activation; noncovalent activation; Asymmetric catalysis is

Synthesis and late stage modifications of Cyl derivatives

• Phil Servatius and
• Uli Kazmaier

Beilstein J. Org. Chem. 2022, 18, 174–181, doi:10.3762/bjoc.18.19

• degree of variability for the generation of small libraries, in our case of Cyl-1 derivatives. Chiral allylic alcohols are easily accessible, either via kinetic resolution of racemic alcohols [46][47], asymmetric catalysis [48], or from chiral pool materials, such as threitol 1 [49]. Using the last