The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• successful employment of amines as nucleophiles for the epoxy ring opening in a highly stereoselective fashion, we next turned our attention to thiols. Optimization of the reaction conditions based on the ones for amines clarified the tendency that the longer reaction time and the higher temperature

• was confirmed as 2,3-anti-3,4-syn by its X-ray crystallographic analysis [49] (Figure 2) whose construction could be readily understood as the result of a highly stereoselective SN2-type epoxy ring opening of 2a, followed by the intramolecular lactone formation with the pro-R ethoxycarbonyl group

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

• proved ineffective in facilitating the Michael addition of bisthiomalonates to conjugated ketones, whereas DABCO enabled the formation of desired products under mild conditions [30]. However, reports of highly stereoselective protocols utilizing hydrogen bonding catalysis have mainly focused on

• -based catalytic system for the highly stereoselective addition of various bisthiomalonates to chalcones and dienones [29]. While recognizing the potential for greater selectivity enhancement and time savings with ball milling, hydrogen-bonding catalysis was effective only with aromatic enones, yielding

Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

• superior results compared to phenyl-substituted compounds. Frank et al. synthesized a series of 16-spiroisoxazolines through a regio- and a highly stereoselective 1,3-dipolar cycloaddition between the double bond of the α,β-unsaturated steroidal ketone 73 and various arylnitrile oxides [45]. The reaction

Trifluoromethylated hydrazones and acylhydrazones as potent nitrogen-containing fluorinated building blocks

• Zhang Dongxu

Beilstein J. Org. Chem. 2023, 19, 1741–1754, doi:10.3762/bjoc.19.127

• =N motif within hydrazones gives them both electrophilic and nucleophilic character. In 2005, Brigaud et al. developed a highly stereoselective method for the synthesis of α-trifluoromethylamines with organometallic reagents to extend the asymmetric methodologies of trifluoroacetaldehyde hydrazones

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• the alkynyl-substituted 1,2-oxazin-4-ol derivative 19 which is smoothly available from the corresponding ketone 6 by highly stereoselective reduction with sodium borohydride [53]. Starting from 1,3- (8) or 1,4-bis(bromomethyl)benzene (16), respectively, the approved conditions in the presence of TBTA

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

• construction of the rings. However, the synthetic methods are still limited, especially for asymmetric synthetic methods. Thus, it is clear that highly stereoselective asymmetric synthetic methods to access various medium and large phostam, phostone, and phostine derivatives are in high demand and should be

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

• stereocenters were isolated in excellent yields and high diastereoselectivity. The authors have shown that catalyst loadings as low as 0.5 mol % can still be sufficient to promote the highly stereoselective reaction. Similarly to aldol reactions, Mannich-type additions are also suitable to trap the metal

• complex molecules by further transformations. Similarly, Huang et al. have recently published their work on the Rh-bod complex-catalyzed highly stereoselective tandem arylation/aldol cyclization [95]. The conjugate addition of arylboronic acids to acyclic α,β-unsaturated ketones 147 with sequential

•  56B) [103]. These complex natural compounds exhibit strong pharmacological activities like anti-inflammatory, antituberculosis, analgesic properties, etc. The key reaction steps included a highly stereoselective gold-catalyzed or thermally activated Cope rearrangement and a gold-catalyzed 6-endo-dig

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

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

• should be noted that the three-step strategy (dithiolane protection, oxidative rearrangement, and hydrodesulfurization) can be used to treat carbonyl functional groups as synthetic equivalents of cis-alkenes (Scheme 10c), as is shown by the highly stereoselective conversion of α-phenylacetophenone (60

Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• + 1] Annulations have been mainly utilized in the construction of the 1,2-azaphospholidine ring, while the [3 + 2] annulation has been seldomly used in the synthesis of pyridine-fused 1,2-azaphospholidine 2-oxide only. Few asymmetric synthetic methods have been developed to date. Thus, highly

• stereoselective asymmetric synthetic methods to access 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides, and their fused and spiro derivatives are in high demand and should be developed in the near future. Biologically active 1,2-azaphospholine 2-oxide derivatives. Diverse synthetic strategies for

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

• ) [59]. The catenane catalyst allows for the asymmetric transfer hydrogenation of 2-substituted quinolines by Hantzsch esters in a highly stereoselective fashion [60]. It was found that the catenated catalyst gives superior stereoselectivities in comparison to the macrocyclic and the acyclic reference

Highly stereocontrolled total synthesis of racemic codonopsinol B through isoxazolidine-4,5-diol vinylation

• Lukáš Ďurina,
• Anna Ďurinová,
• František Trejtnar,
• Ľuboš Janotka,
• Lucia Messingerová,
• Jana Doháňošová,
• Ján Moncol and
• Róbert Fischer

Beilstein J. Org. Chem. 2021, 17, 2781–2786, doi:10.3762/bjoc.17.188

• homoallylic position that assists the electrophilic attack on the double bond [33][34]. The protection of the homoallylic hydroxy group in similar alkenyl diols in epoxidations with the VO(acac)2/t-BuOOH system led to the formation of the erythro isomer [35]. Actually, highly stereoselective epoxidations of

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• study [41][42] in 2017. This metal-catalyzed, photoinduced, and asymmetric radical transformation requires two catalysts, namely, (i) a metal catalyst that promotes electron transfer and (ii) a separate chiral catalyst that facilitates the highly stereoselective bond formation. In 2016, Fu [82

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• acid (4) as catalyst [30]. Based on this pioneer work, our research group described an efficient, highly stereoselective, one-pot process comprising an organocatalytic conjugate addition of dimedone or 4-hydroxycoumarin 1 to α,β-unsaturated aldehydes 2 followed by an intramolecular isocyanide-based

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

Stereoselective synthesis and transformation of pinane-based 2-amino-1,3-diols

• Ákos Bajtel,
• Mounir Raji,
• Matti Haukka,
• Ferenc Fülöp and
• Zsolt Szakonyi

Beilstein J. Org. Chem. 2021, 17, 983–990, doi:10.3762/bjoc.17.80

• carbamate 8 in good yield [27][28][36]. In the next step, the aminohydroxylation was accomplished by potassium osmate(VI) as the catalyst and t-BuOCl in the presence of DIPEA affording oxazolidine-2-one 9 [27]. The reaction was found to be highly stereoselective, giving exclusively the diexo-fused tricyclic

Prins cyclization-mediated stereoselective synthesis of tetrahydropyrans and dihydropyrans: an inspection of twenty years

• Asha Budakoti,
• Pradip Kumar Mondal,
• Prachi Verma and
• Jagadish Khamrai

Beilstein J. Org. Chem. 2021, 17, 932–963, doi:10.3762/bjoc.17.77

• cyclization and minimizes the competitive 2-oxonia-[3,3]-sigmatropic rearrangement pathway. The reaction was highly stereoselective and afforded the cis-2,6-dihydropyran in the presence of Lewis acid FeCl3. From DFT calculations, the authors concluded that the Prins product is formed more rapidly than the α

• (Scheme 60). Competition between electronically favored transition state 254 leads to the formation of anti-isomer 256, whereas the sterically preferred transition state 255 afforded syn-isomer 257. Unlike the well-explored selective synthesis of major cis-2,6-THP, a highly stereoselective route to the

Synthetic strategies of phosphonodepsipeptides

• Jiaxi Xu

Beilstein J. Org. Chem. 2021, 17, 461–484, doi:10.3762/bjoc.17.41

• phosphonodepsipeptides in the future. However, highly stereoselective asymmetric synthetic methods of phosphonodepsipeptides are of high demand and need to be developed in the near future. Phosphonopeptides, phosphonodepsipeptides, peptides, and depsipeptides. The diverse strategies for phosphonodepsipeptide synthesis

Au(III) complexes with tetradentate-cyclam-based ligands

• Ann Christin Reiersølmoen,
• Thomas N. Solvi and
• Anne Fiksdahl

Beilstein J. Org. Chem. 2021, 17, 186–192, doi:10.3762/bjoc.17.18

• trans product. Thus, the proper choice of the gold catalyst allows highly stereoselective formation of either cis or trans cyclopropanation products and facilitates the isolation of pure isomers. Despite the chiral nature of these ligands, no enantioselectivity was observed in the test reactions

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• highly stereoselective, this relatively lengthy route was somewhat inefficient (16 steps, 1.4% overall yield). The Nicolaou synthesis [24][25] of the C-1–C-9 tetrahydropyranyl segment commenced with the protected dihydropyranone 103 (Scheme 17), readily prepared from ᴅ-glucal [38]. The application of an

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• ) reacted with electron-poor olefins, such as acrylonitrile (187b), methyl acrylate (187c), and cis- and trans-1,2-dichloroethenes 188, under photochemical conditions, giving 2-silylthietanes 317 and 318 in a regio- and highly stereoselective manner. However, silyl thietanes without any regio- or