Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds

• Natalya Akhmetdinova,
• Ilgiz Biktagirov and
• Liliya Kh. Faizullina

Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185

• % yield. Jin et al. [85] reported an efficient photoinduced carboborative ring contraction of monounsaturated six-membered carbo- and heterocycles, allowing the regio- and stereoselective synthesis of functionalized cyclopentanes at gram scales. This method leads to the formation of compounds with

• to the reaction mixture protected the aldehyde group as a dioxolane, providing cyclopentane 227 with a yield of 79% in two steps (Scheme 40). In the alternative stereoselective synthesis of (−)-spirochensilide A (228), proposed by Liang et al. [98], one of the key steps was the semipinacol

Recent advances in Norrish–Yang cyclization and dicarbonyl photoredox reactions for natural product synthesis

• Peng-Xi Luo,
• Jin-Xuan Yang,
• Shao-Min Fu and
• Bo Liu

Beilstein J. Org. Chem. 2025, 21, 2315–2333, doi:10.3762/bjoc.21.177

• can further undergo ring-opening or rearrangement reaction to assemble complex molecular frameworks. Additionally, quinone photoredox reactions involving single-electron transfer (SET) processes provide novel strategies for the stereoselective synthesis of useful structures such as spiroketals. This

A chiral LC–MS strategy for stereochemical assignment of natural products sharing a 3-methylpent-4-en-2-ol moiety in their terminal structures

• Rei Suo,
• Raku Irie,
• Hinako Nakayama,
• Yuta Ishimaru,
• Yuya Akama,
• Masato Oikawa and
• Shiro Itoi

Beilstein J. Org. Chem. 2025, 21, 2243–2249, doi:10.3762/bjoc.21.171

• the MPO moiety by LC–MS and demonstrate its application to the stereochemical assignment of capsulactone (1) at the microgram scale. The strategy involves the optical resolution of MPO derivatives, chemical degradation of 1, and the stereoselective synthesis of four diastereomers. Results and

• that at C8–C9, and (3) methyl esterification (Scheme 2). The resulting C9–C12 fragment 7 was successfully detected at m/z 304.1 [M + Na]+ by LC–MS, as expected (see Figure 2b for the chromatogram). We then proceeded with the stereoselective synthesis of four diastereomers; 4-methoxy-3-methyl-4-oxobutan

Understanding the origin of stereoselectivity in the photochemical denitrogenation of 2,3-diazabicyclo[2.2.1]heptene and its derivatives with non-adiabatic molecular dynamics

• Leticia A. Gomes and
• Steven A. Lopez

Beilstein J. Org. Chem. 2025, 21, 2007–2020, doi:10.3762/bjoc.21.156

• nucleophiles [7][8][9][10][11], radicals [12][13][14][15] and electrophiles [16][17][18] to give cyclobutanes and cyclobutenes [19][20], which are building blocks in regio- and stereoselective synthesis [21][22][23][24][25][26][27] (Scheme 1a). Additionally, BCB has been used in bioconjugation due to its high

• been employed to release carbon monoxide at relatively safer doses in biological systems using photoresponsive CO-releasing molecules (photo-CORMs) [4] because these have shown anti-inflammatory activity [5][6]. Photochemical denitrogenation of azoalkanes has been utilized in the stereoselective

• synthesis of strained compounds such as bicyclo[1.1.0]butane (BCB) and bicyclo[2.1.0]pentane (housane). The energy stored in strained σCC bonds of BCB and housane makes them important building blocks in the synthesis of complex molecular structures. BCBs have been employed in ring-opening reactions with

Stereoselective electrochemical intramolecular imino-pinacol reaction: a straightforward entry to enantiopure piperazines

• Margherita Gazzotti,
• Fabrizio Medici,
• Valerio Chiroli,
• Laura Raimondi,
• Sergio Rossi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2025, 21, 1897–1908, doi:10.3762/bjoc.21.147

• products, agrochemicals, and pharmacologically active compounds. Enantiomerically pure 1,2-diamines and their derivatives are also increasingly used in stereoselective synthesis, particularly as chiral auxiliaries or as ligands for metal complexes in asymmetric catalysis [1]. Metal-based reductants

Approaches to stereoselective 1,1'-glycosylation

• Daniele Zucchetta and
• Alla Zamyatina

Beilstein J. Org. Chem. 2025, 21, 1700–1718, doi:10.3762/bjoc.21.133

• precursors [38][39][40][41][42]. This emphasizes the importance of reliable and reproducible approaches for the stereoselective synthesis of unsymmetrically orthogonally protected nonreducing disaccharides. While the desired anomeric selectivity on the side of the glycosyl donor can often be achieved by

Copper catalysis: a constantly evolving field

• Elena Fernández and
• Jaesook Yun

Beilstein J. Org. Chem. 2025, 21, 1477–1479, doi:10.3762/bjoc.21.109

• stereoselective synthesis of chlorocyclopropanes. As guest editors, we are deeply grateful to all contributors for sharing their high-quality work and valuable perspectives. We also thank the referees for their thoughtful evaluations, which helped maintain the scientific rigor of this collection. We hope this

Recent advances in synthetic approaches for bioactive cinnamic acid derivatives

• Betty A. Kustiana,
• Galuh Widiyarti and
• Teni Ernawati

Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85

Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

• Patricia Gómez-Roibás,
• Andrea Chaves-Pouso and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

• versatile building blocks for the stereoselective synthesis of chlorocyclopropanes. Keywords: chlorocyclopropanes; copper; cyclization; 4,4-dichloro-2-butenoic acid derivatives; dimerization; Introduction In the last years our group has been focused on the development of catalytic methodologies for the

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• diastereomerically pure γ‑branched fluorinated amino acids. This work further underlines the importance of chiral Ni(II) complexes in the synthesis of fluorinated amino acids. Keywords: chiral nickel complexes; fluorinated amino acids; gram-scale amino acid synthesis; stereoselective synthesis; Introduction Non

Vinylogous functionalization of 4-alkylidene-5-aminopyrazoles with methyl trifluoropyruvates

• Judit Hostalet-Romero,
• Laura Carceller-Ferrer,
• Gonzalo Blay,
• Amparo Sanz-Marco,
• José R. Pedro and
• Carlos Vila

Beilstein J. Org. Chem. 2025, 21, 533–540, doi:10.3762/bjoc.21.41

• functionalize 5-aminopyrazoles. Biologically active compounds featuring a trifluoromethyl carbinol motif. Nucleophilic sites of 5-aminopyrazoles and 4-alkenyl-5-aminopyrazoles. Stereoselective synthesis of trifluoromethyl carbinols through an vinylogous addition reaction of 4-alkenyl-5-aminopyrazoles to alkyl

Diastereoselective synthesis of highly substituted cyclohexanones and tetrahydrochromene-4-ones via conjugate addition of curcumins to arylidenemalonates

• Deepa Nair,
• Abhishek Tiwari,
• Banamali Laha and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2024, 20, 2016–2023, doi:10.3762/bjoc.20.177

• considerable interest in the stereoselective synthesis of the cyclohexanone skeleton as it constitutes the core structure in many natural products and pharmaceutical drugs [1][2]. Garsubellin A with a cyclohexanone skeleton is a potent inducer of choline acetyltransferase (ChAT) and could be used for the

Bismuth(III) triflate: an economical and environmentally friendly catalyst for the Nazarov reaction

• Manoel T. Rodrigues Jr.,
• Aline S. B. de Oliveira,
• Ralph C. Gomes,
• Amanda Soares Hirata,
• Lucas A. Zeoly,
• Hugo Santos,
• João Arantes,
• Catarina Sofia Mateus Reis-Silva,
• João Agostinho Machado-Neto,
• Leticia Veras Costa-Lotufo and
• Fernando Coelho

Beilstein J. Org. Chem. 2024, 20, 1167–1178, doi:10.3762/bjoc.20.99

• lilolidone nucleus [77] and by Jung in the stereoselective synthesis of podophyllotoxin derivatives (Scheme 1) [78]. Although the decarboxylation reaction of indanones has been observed and described in the literature, there are few extensive studies aimed at exploring this transformation. The only exception

A novel recyclable organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen

• Gyula Dargó,
• Dóra Erdélyi,
• Balázs Molnár,
• Péter Kisszékelyi,
• Zsófia Garádi and
• József Kupai

Beilstein J. Org. Chem. 2023, 19, 1811–1824, doi:10.3762/bjoc.19.133

• organocatalysts has been a major breakthrough in the realization of enantioselective transformations. Stereoselective synthesis is essential in the pharmaceutical industry, as the development of drugs often requires the production of enantiomerically pure chiral compounds [6][7][8]. The application of

• cinchona squaramide organocatalyst. Its catalytic activity and recyclability were examined in a new stereoselective synthesis of baclofen, which is used to treat muscle spasms [30]. Finally, the catalyst was easily recycled by centrifugation over five reaction cycles without significant loss of activity

• literature [41]. Application of cinchona squaramide 1 and recyclable, lipophilic cinchona squaramide organocatalysts 2 in a new, gram-scale stereoselective synthesis of baclofen precursor. Classification of the tested non-polar solvents according to the GSK’s solvent sustainability guide [34]. Recycling of

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• NaH, DMF) were applied to prepare enantiopure (R)-6.1 or (S)-6.1 from commercially available enantiopure solketal [75][76][78]. For the protected secondary alcohol of the glycerol derivative 6.6a (Figure 6B), a stereoselective synthesis, starting from either ᴅ- or ʟ-tartaric acids, produced first the

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• . Except lately, in 2020, Chen and group [82] reported a Pd/Cu-catalyzed regio- and stereoselective synthesis of C2-alkenylated pyridines starting from internal alkynes 84 and pyridinium salts in a stereodivergent manner (Scheme 17a). The interesting part of this work was the switching of the alkene

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

• contains six contiguous stereogenic centers out of which four are all-carbon quaternary stereocenters. The authors have achieved the stereoselective synthesis of waihoensene for the first time with a 3.8% overall yield (15 steps) (Scheme 59). The construction of the triquinane core included a Cu-catalyzed

• in the first step by the phosphoramidite ligand L39 (92% ee, dr 1:1) (Scheme 60). Recently, Liu and co-workers reported the stereoselective synthesis of the tricyclic core of dodecahydrodibenzo[b,d]furan skeleton containing 12-epi-JBIR-23 and -24 [111]. Besides their intriguing complex structures

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• base chiral template is a fairly versatile “tool” that can be adapted to a specific task. A relatively new approach to functionalization of amino acids is a combination of a stereoselective synthesis in a metal-coordination environment with electrochemical activation [31]. It increases the reactivity

• new ligand and amino acids (glycine and dehydroalanine) will find their rightful place in the stereoselective synthesis of tailor-made amino acids (including oxidative transformations). Fragment of the NOESY spectrum of the ʟ-(oBrCysNi)L7 complex indicating the correlation between the H-2 and H-17,21

Asymmetric synthesis of a stereopentade fragment toward latrunculins

• Benjamin Joyeux,
• Antoine Gamet,
• Nicolas Casaretto and
• Bastien Nay

Beilstein J. Org. Chem. 2023, 19, 428–433, doi:10.3762/bjoc.19.32

• precluded the installation of the pyran ring – and the use of its well-known isomerization to set up important stereocenters [6][9] –, thus imposing the anticipated construction of key asymmetric centers. The following discussion will deal with the stereoselective synthesis of a stereopentade amenable to

Total synthesis of insect sex pheromones: recent improvements based on iron-mediated cross-coupling chemistry

• Eric Gayon,
• Guillaume Lefèvre,
• Olivier Guerret,
• Adrien Tintar and
• Pablo Chourreu

Beilstein J. Org. Chem. 2023, 19, 158–166, doi:10.3762/bjoc.19.15

• issues for living organisms [25][26]. Additionally, the classic stereoselective synthesis of dienol phosphates requires cryogenic temperatures (−78 °C) as well as NMP-based methodologies [27]. Therefore, motivated by those considerations, we sought a suitable efficient and non-toxic additive which would

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• formation of the cis-vinylcyclopropanes (Scheme 18c and 18d). Desulfurization of the adducts again yields the product of a formal cyclopropanation with a ‘naked’ vinyl carbene species, as demonstrated by the stereoselective synthesis of the protected cis-2-vinylcyclopropan-1-amine 123 (Scheme 18d). 7

• ][57]. Stereoselective 5,6-dihydro-1,4-dithiin-based synthesis of cis-olefins [42][58]. Addition to aldehydes and applications in stereoselective synthesis. Direct C–H functionalization methods for 1,4-dithianes [82][83]. Known cycloaddition reactivity modes of allyl cations [84][85][86][87][88][89][90

Synthetic study toward the diterpenoid aberrarone

• Liang Shi,
• Zhiyu Gao,
• Yiqing Li,
• Yuanhao Dai,
• Yu Liu,
• Lili Shi and
• Hong-Dong Hao

Beilstein J. Org. Chem. 2022, 18, 1625–1628, doi:10.3762/bjoc.18.173

• . Impressed by the structural features and biological profiles, our group embarked a project on the total synthesis of this natural product. Herein, we report our stereoselective synthesis of its 6-5-5 tricyclic skeleton. Our retrosynthetic analysis is shown in Scheme 1. For the formation of the D ring with

First total synthesis of hoshinoamide A

• Haipin Zhou,
• Zihan Rui,
• Yiming Yang,
• Shengtao Xu,
• Yutian Shao and
• Long Liu

Beilstein J. Org. Chem. 2021, 17, 2924–2931, doi:10.3762/bjoc.17.201

• synthesized in high efficiency. After systematic screening of the coupling reagents in liquid phase, the key intermediate tripeptide 7 was obtained in high yield. The solid-phase synthesis improves the entire efficiency of the synthetic route. This strategy could be applied to the stereoselective synthesis of

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

• Tomáš Chvojka,
• Athanasios Markos,
• Svatava Voltrová,
• Radek Pohl and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 2657–2662, doi:10.3762/bjoc.17.179

• isomerization of N-allyl amides [20], but still possess drawbacks, especially for stereoselective synthesis of tri- and tetrasubstituted enamides. Recently, we have reported a triflic acid-mediated reaction of N-fluoroalkyl-1,2,3-triazoles leading to (Z)-β-enamido triflates [21] and Lewis acid-mediated reaction

• configuration of the double bond were formed preferably. Both conditions were applied to a range of arylboronic acids and (Z)-β-enamido triflates. A: Synthesis of (Z)-β-enamido triflates and subsequent stereoselective cross-coupling reactions. B: Ligand-controlled stereoselective synthesis of β,β-diaryl

Solvent-free synthesis of enantioenriched β-silyl nitroalkanes under organocatalytic conditions

• Akhil K. Dubey and
• Raghunath Chowdhury

Beilstein J. Org. Chem. 2021, 17, 2642–2649, doi:10.3762/bjoc.17.177

• Enantioenriched organosilanes are attractive molecules in organic synthesis owing to their potential applications in stereoselective synthesis [1][2]. The unique sterical and electronical features of the C–Si bond can induce stereodifferentiation at the adjacent prostereogenic center in organic transformations [2