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Search for "asymmetric" in Full Text gives 926 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Thiazolidinones: novel insights from microwave synthesis, computational studies, and potentially bioactive hybrids
Beilstein J. Org. Chem. 2025, 21, 2618–2636, doi:10.3762/bjoc.21.203
- crystal XRD analysis confirmed the presence of the expected products and the stereochemistry of the newly created olefinic compound as being Z, as expected. Compound 3n crystallizes in the monoclinic crystal system with four molecules in the asymmetric unit whereas 4n crystallizes in the triclinic crystal
- system with two molecules in the asymmetric unit. The bond distances in 3n C1=O1 is 1.229(4) Å and C2=S2 is 1.629(4) Å. For compound 4n, the observed C=O bond length is shorter than that of compound 3n (1.202(2) and 1.221(2) Å), respectively (Supporting Information File 1, Table S3). Intermolecular
Visible-light-driven NHC and organophotoredox dual catalysis for the synthesis of carbonyl compounds
Beilstein J. Org. Chem. 2025, 21, 2584–2603, doi:10.3762/bjoc.21.200
- asymmetric reactions and are functional transformations in synthetic organic chemistry. Especially, 1,2,3-triazole-based NHCs are generally more reactive and stronger σ-donors than imidazole or thiazole analogues. Triazolium NHC enhances their ability to stabilize reactive radical intermediates or acyl anion
- , Michael additions, cycloadditions, domino reactions, cascade annulations, Diels–Alder reactions, and Michael–Stetter reactions, to name a few [31][32][33][34][35]. Notably, previous reports have demonstrated that the utility of chiral N-heterocyclic carbene (NHC) catalysts permits contracting asymmetric C
- and heteroarenes using blue LED. Asymmetric synthesis of fused pyrrolidinones via organophotoredox/N‑heterocyclic carbene dual catalysis. Acknowledgements Vasudevan Dhayalan expresses his appreciation to DST-SERB for core research grant (CRG/2022/001855), and to the National Institute of Technology
Recent advances in total synthesis of illisimonin A
Beilstein J. Org. Chem. 2025, 21, 2571–2583, doi:10.3762/bjoc.21.199
- was conclusively revised to 1S,4S,5S,6S,7R,9R,10R. Kalesse’s asymmetric synthesis of illisimonin A In 2023, Kalesse and co-workers reported an asymmetric synthetic route to illisimonin A [29]. The Kalesse group also noticed the strained trans-pentalene in illisimonin A. Since there is a spiro
- hydroxy group could be responsible for this reversal in selectivity. Dai’s asymmetric synthesis of (−)-illisimonin A In 2025, Dai and co-workers accomplished an asymmetric total synthesis of (−)-illisimonin A in 16 steps from (S)-carvone (67) using a pattern-recognition strategy and five sequential olefin
- encumbered tricyclic lactone 84 via an intramolecular [6 + 2] cycloaddition (Scheme 8). Attempts to achieve an asymmetric version of the cycloaddition were unsuccessful. Treatment of the lactone with MeMgBr, followed by mesylation and elimination of the resulting hemiacetal, afforded enol ether 85. Reaction
Total syntheses of highly oxidative Ryania diterpenoids facilitated by innovations in synthetic strategies
Beilstein J. Org. Chem. 2025, 21, 2553–2570, doi:10.3762/bjoc.21.198
- core, successfully completing the first asymmetric total synthesis of ryanodol (4) in 41 steps. To elucidate the role of the C15 hemiacetal hydroxy group in ryanodine (1)-type diterpenoid natural products in binding to ryanodine receptors, the authors initially proposed reducing the lactone moiety in
- ). Furthermore, from intermediate 57, the introduction of an isopropyl group at C2 and subsequent deprotection furnished cinnzeylanol (6). Reisman’s total synthesis of (+)-ryanodine (1), (+)-20-deoxyspiganthine (2), and (+)-ryanodol (4) In 2016, the Reisman group at Caltech reported an asymmetric total synthesis
- , epoxidation of the C1–C2 double bond, and Li/NH3-promoted reductive cyclization to construct the core E ring, completing the asymmetric total synthesis of (+)-ryanodol (4). The 800-fold greater binding affinity of (+)-ryanodine (1) for cardiac ryanodine receptors (RyRs) compared to its hydrolysis product
Ni-promoted reductive cyclization cascade enables a total synthesis of (+)-aglacin B
Beilstein J. Org. Chem. 2025, 21, 2548–2552, doi:10.3762/bjoc.21.197
- Abstract The total synthesis of bioactive (+)-aglacin B was achieved. The key steps include an asymmetric conjugate addition reaction induced by a chiral auxiliary and a nickel-promoted reductive tandem cyclization of the elaborated β-bromo acetal, which led to the efficient construction of the
- synthesis of both enantiomers of aglacins A (1), B (2), and E (4) by asymmetric photoenolization/Diels–Alder reactions as the key steps for the construction of the C7–C8 and C7′–C8′ bonds [8]. During the past decade, we had developed nickel-catalyzed or -promoted reductive coupling/cyclization reactions for
- that the diarylmethine stereocenter at C7′ in 6 could be formed by an Evans’ auxiliary-induced asymmetric conjugate addition of α,β-unsaturated acyl oxazolidinone 7 with 3,4,5-trimethoxyphenylmagnesium bromide (8). Both of these two building blocks could be conveniently prepared from commercially
Catalytic enantioselective synthesis of selenium-containing atropisomers via C–Se bond formations
Beilstein J. Org. Chem. 2025, 21, 2447–2455, doi:10.3762/bjoc.21.186
- Atropisomers are not only prevalent in biologically active natural products and pharmaceuticals, but they have also garnered increasing attention for their effectiveness as ligands and catalysts in the field of catalytic asymmetric synthesis. Asymmetric catalysis serves as a key strategy for the
- . Keywords: asymmetric catalysis; atropisomer; chiral selenium-containing compound; C–Se bond formation; Introduction Selenium is an essential trace element for human body [1]. It plays an important role in metabolism. In 1817, the Swedish chemist Berzelius found that red residual mud was attached to the
- compounds can participate in asymmetric synthesis reactions and construct chiral molecules with specific stereoconfiguration, which is particularly critical for drug synthesis [9]. In the field of organic catalysis, chiral organic selenium-containing compounds can be used as chiral ligands or catalysts to
Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds
Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185
- (III) and iodine(III), and Wolff rearrangement. 2.1 Benzilic acid and semipinacol-type rearrangements The strategy of ring contraction using the benzilic acid-type rearrangement was used by Zhang et al. [38] for the asymmetric synthesis of 4β-acetoxyprobotryane-9β,15α-diol (52). This compound contains
- aldehyde 53 [39] (Scheme 10). The key steps in this synthesis are based on an asymmetric rhodium-catalyzed [4 + 2] cycloaddition reaction [40], followed by a unique benzilic acid-type rearrangement under very mild conditions [41]. A step-by-step mechanism for the benzilic acid-type rearrangement of
An Fe(II)-catalyzed synthesis of spiro[indoline-3,2'-pyrrolidine] derivatives
Beilstein J. Org. Chem. 2025, 21, 2383–2388, doi:10.3762/bjoc.21.183
- cyclization. Subsequently Zhong et al. reported a catalytic asymmetric variant, affording spirooxindoles in high yields with excellent enantioselectivity [8]. An alternative approach employing vinyl azides involves a Rh(II)-catalyzed olefination of diazo compounds, followed by annulation with vinyl azides to
Synthetic study toward vibralactone
Beilstein J. Org. Chem. 2025, 21, 2376–2382, doi:10.3762/bjoc.21.182
- late-stage lactonization as key steps [26] (Scheme 1). Subsequently, they achieved the asymmetric synthesis of vibralactone (6) based on the asymmetric Birch reduction–alkylation methodology developed by the Schultz group [27][28]. In 2016, Brown and co-workers described an efficient synthetic route
Adaptive experimentation and optimization in organic chemistry
Beilstein J. Org. Chem. 2025, 21, 2367–2368, doi:10.3762/bjoc.21.180
- human–AI synergy emerges repeatedly. The computational design of asymmetric catalysts by Ferrer et al. demonstrates how AI can accelerate discovery while relying on chemical principles to guide the search space [14]. The most successful approaches combine the rapid exploration capabilities of AI with
Rotaxanes with integrated photoswitches: design principles, functional behavior, and emerging applications
Beilstein J. Org. Chem. 2025, 21, 2345–2366, doi:10.3762/bjoc.21.179
- patterns that dictate the position of the macrocycle. Later, Leigh and co-workers introduced a new strategy for dynamically controlling asymmetric catalysis using a hydrazone-based rotaxane [72]. The axle features a hydrazone photoswitch and a pseudo-meso 2,5-disubstituted pyrrolidine organocatalytic unit
- group reported related [2]rotaxanes in which stilbene trans-to-cis photoisomerization induced the translocation of the cyclodextrin along the axle [77]. Remarkably, the movement of the macrocycle was unidirectional, driven by the asymmetric size difference between the two rims of the cyclodextrin
- , Yang and co-workers reported a [2]rotaxane featuring a macrocycle constructed from two azobenzene photoswitches threaded onto an asymmetric axle [89]. Photoisomerization of the azobenzenes alters the geometry and size of the macrocycle, thereby modulating its affinity toward two distinct recognition
Recent advances in Norrish–Yang cyclization and dicarbonyl photoredox reactions for natural product synthesis
Beilstein J. Org. Chem. 2025, 21, 2315–2333, doi:10.3762/bjoc.21.177
- intramolecular aldehyde α-alkylation using MacMillan's protocol, subsequently undergoing Shi's asymmetric epoxidation to give rise to epoxide 60 as a 3:1 mixture of diastereomers. These were not separated until step 8 due to poor separability at this stage. Concurrently, diosgenin was then processed through a
- . Asymmetric total synthesis of lycoplatyrine A. Photoreaction of pyrrolidine-derived phenyl keto amide. Photoredox reactions of naphthoquinones. Synthetic study toward γ-rubromycin. Substituent-dependent conformational preferences. Total synthesis of preussomerins EG1, EG2, and EG3. Acknowledgements This
Insoluble methylene-bridged glycoluril dimers as sequestrants for dyes
Beilstein J. Org. Chem. 2025, 21, 2302–2314, doi:10.3762/bjoc.21.176
- /Å = 16.050(5); c/Å = 18.165(5); α/° = 64.669(7), β/° = 69.128(6), γ/° = 76.782(7)). Figure 6a shows a cross-eyed stereoview of G2W1 in the asymmetric unit of the crystal. Similar to that observed for G2W3, the G2W1 molecules undergo a splaying of their triphenylene walls. This splayed geometry
Enantioselective radical chemistry: a bright future ahead
Beilstein J. Org. Chem. 2025, 21, 2283–2296, doi:10.3762/bjoc.21.174
- describes several important catalytic asymmetric strategies applied to enantioselective radical reactions, including chiral Lewis acid catalysis, organocatalysis, photoredox catalysis, chiral transition-metal catalysis and photoenzymatic catalysis. The application of electrochemistry to asymmetric radical
- transformations is also discussed. Keywords: chiral Lewis acid; electrochemistry; enantioselective radical reaction; organocatalysis; photoenzymatic catalysis; photoredox; Introduction Asymmetric catalysis plays an integral role in the enantioselective synthesis of organic compounds. A wide variety of
- the 1990s. Since then, meticulous research by several research groups has led to significant advances in this area [4][5][6][7][8]. This perspective focuses on several important contributions to the science of asymmetric radical reactions. Pioneering work on chiral Lewis acid catalysis and iminium
Thiadiazino-indole, thiadiazino-carbazole and benzothiadiazino-carbazole dioxides: synthesis, physicochemical and early ADME characterization of representatives of new tri-, tetra- and pentacyclic ring systems and their intermediates
Beilstein J. Org. Chem. 2025, 21, 2220–2233, doi:10.3762/bjoc.21.169
- performed using the method described in the literature [18], i.e., by heating compounds 5a,b with ketones 6a–e in the presence of bismuth nitrate pentahydrate catalyst and PPA in methanol at 110 °C in a closed vial (Scheme 1, method B). In the synthesis of asymmetric hydrazones 7a,c,f,h, the major product
- 7c compared to 7b is likely due to the structural differences, with 7a and 7c having asymmetric substitutions (methyl for 7c, R2 = H, R3 = Me and ethyl, methyl for 7a, R2 = Me, R3 = Me), while 7b having a symmetric diethyl substitution pattern (R2 = Et, R3 = Me). The comparison of the solubility of
C2 to C6 biobased carbonyl platforms for fine chemistry
Beilstein J. Org. Chem. 2025, 21, 2103–2172, doi:10.3762/bjoc.21.165
- catalysts including Ni/CeO2-γAl2O3, spinal NiAl2O4 and Ni/La2O3-αAl2O3, at 230 °C and 3.2 MPa. Using a chiral catalyst composed of [RuCl2(benzene)]2 and SunPhos, an effective asymmetric hydrogenation of α-hydroxy ketones was reported, yielding chiral terminal 1,2-diols in up to 99% ee. This Ru-catalyzed
- asymmetric hydrogenation process of α-hydroxy ketones opens up a new pathway for the production of chiral terminal 1,2-diols (Scheme 23) [98]. Kini and Mathews reported the synthesis of novel oxazole derivatives such as 6-(substituted benzylidene)-2-methylthiazolo[2,3-b]oxazol-5(6H)-one by reacting 1
- MPa NH3 and 2 MPa H2. The reaction could be carried for 10 catalytic cycles without deactivation. Zhang developed a transition-metal copper-catalyzed chemoselective asymmetric hydrogenation of the carbonyl group in exocyclic α,β-unsaturated cyclopentanones. Chiral exocyclic allylic pentanols (a
The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products
Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164
- shortage of natural product sources. Nevertheless, the asymmetric total synthesis of terpenoid and alkaloid natural products presents significant challenges due to their complex and diverse ring systems and the presence of multiple stereocenters, including all-carbon quaternary stereocenters. Consequently
- , the development of novel methods and strategies to achieve efficient asymmetric total synthesis of complex terpenoid and alkaloid natural products has drawn considerable attention from synthetic chemists. Over the past decades, the development of desymmetric enantioselective reduction strategy of
- co-workers accomplished the first asymmetric total synthesis of (+)-aplysiasecosterol A (6) by employing a desymmetric enantioselective reduction strategy of 1,3-cyclopentanedione derivative as the key transformation [14]. Their synthesis features a highly efficient desymmetric enantioselective
Bioinspired total syntheses of natural products: a personal adventure
Beilstein J. Org. Chem. 2025, 21, 2048–2061, doi:10.3762/bjoc.21.160
- catalytic asymmetric methods [26], we intended to probe this biomimetic oxidative cyclization transformation [27][28]. In 2013, we first used monocerin as a model target molecule to initiate our study (Scheme 3a). Starting from benzaldehyde 11 with an isopropyl group on the hydroxy group in 4-position
- powerful routes to the asymmetric total synthesis of these bioactive molecules. The precursors of the key bioinspired transformations 36, 38 and 40 were efficiently synthesized from simple fragments aryl aldehyde 42 or 43, phenylboronic acid 44 and chiral auxiliary-containing building block 45, through
Measuring the stereogenic remoteness in non-central chirality: a stereocontrol connectivity index for asymmetric reactions
Beilstein J. Org. Chem. 2025, 21, 1995–2006, doi:10.3762/bjoc.21.155
- Ivan Keng Wee On Yu Kun Choo Sambhav Baid Ye Zhu Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 2, Singapore 117543 10.3762/bjoc.21.155 Abstract Despite the rapid development of asymmetric synthesis, judging the remoteness of stereocontrol has
- remained an intuitive and empirical practice, particularly for reactions that create non-central chirality. We put forward a stereocontrol connectivity index to parameterize asymmetric reactions according to the bond connectivity relationships between the prochiral stereogenic elements, the reactive sites
- chiral molecules. Keywords: asymmetric reactions; axial chirality; catalysis; planar chirality; stereocontrol; Introduction Chirality is a ubiquitous and fundamental phenomenon in nature and thus holds an irreplaceable position in organic synthesis. At its most rudimental definition, chirality in a
Asymmetric total synthesis of tricyclic prostaglandin D2 metabolite methyl ester via oxidative radical cyclization
Beilstein J. Org. Chem. 2025, 21, 1964–1972, doi:10.3762/bjoc.21.152
- available has prevented its practical use, and synthesis methods for tricyclic-PGDM methyl ester are required. Based on the utilization of oxidative radical cyclization for the stereoselective construction of the cyclopentanol subunit with three consecutive stereocenters, we describe an asymmetric total
- synthesis of tricyclic-PGDM methyl ester in 9 steps and 8% overall yield. Keywords: asymmetric total synthesis; oxidative radical cyclization; tricyclic prostaglandin D2 metabolite methyl ester; Introduction Prostaglandins (PGs), a family of hormone-like lipid compounds, are ubiquitous natural products
- ring system with the appropriate functional groups in place for attaching the remaining groups is a highly important task for the asymmetric total synthesis of PGs and analogues [10][11][12][13]. The groups of Aggarwal [14], Hayashi [15], and Zhang [16] have reported bond-disconnection strategies for
Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis
Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151
- biologically active molecules. Based on the reaction types, three strategies are discussed: enzymatic acylation, transition-metal-catalyzed acylation, and local desymmetrization. Keywords: asymmetric synthesis; desymmetrization; 1,3-diols; natural product; total synthesis; Introduction Natural products
- isolated from organisms are often asymmetric in their spatial structures, and these unique spatial structures are precisely what lead to their diverse biological activities [1][2][3][4]. For the synthesis of these natural products or bioactive molecules, chemists usually need to consider how to carry out
- asymmetric synthesis of them, driving the advancement of asymmetric methodologies [5][6][7][8][9]. Enantioselective desymmetrization of symmetric substrates has emerged as a pivotal methodology for the construction of chiral centers over the past few decades [10][11][12][13]. A series of reaction types have
Synthesis of N-doped chiral macrocycles by regioselective palladium-catalyzed arylation
Beilstein J. Org. Chem. 2025, 21, 1917–1923, doi:10.3762/bjoc.21.149
- that inherently lacks symmetry [8][9]. One of the most typical representatives are calix[4]arenes (Figure 1a), first reported by Böhmer in 1994 [10], where asymmetric substitutions on the macrocyclic rim induce inherent chirality. Subsequent advancements have identified other inherent chiral systems
- asymmetric geometry due to the fusion of the pyrene unit (Figure 2c). The two pyrene units are oriented antiparallel, which is distinctive from that observed in 3a and MC2. Notably, the pyrene-fused moiety is highly curved with a bending angle of 85.3° as defined by the angle of the planes of the terminal
Stereoselective electrochemical intramolecular imino-pinacol reaction: a straightforward entry to enantiopure piperazines
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
Chiral phosphoric acid-catalyzed asymmetric synthesis of helically chiral, planarly chiral and inherently chiral molecules
Beilstein J. Org. Chem. 2025, 21, 1864–1889, doi:10.3762/bjoc.21.145
- with the more recently introduced inherent chirality. As one of the most prominent chiral organocatalysts, chiral phosphoric acid (CPA) catalysis has proven highly effective in synthesizing centrally and axially chiral molecules. However, its potential in the asymmetric construction of other types of
- molecular chirality has been investigated comparatively less. This Review provides a comprehensive overview of the recent emerging advancements in asymmetric synthesis of planarly chiral, helically chiral and inherently chiral molecules using CPA catalysis, while offering insights into future developments
- within this domain. Keywords: asymmetric catalysis; chiral phosphoric acid; helical chirality; inherent chirality; planar chirality; Introduction Since the seminal works by Akiyama [1] and Terada [2] et al. in 2004 demonstrated the application of BINOL-derived chiral phosphoric acids (CPAs) in
Photoswitches beyond azobenzene: a beginner’s guide
Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143
- , bottom), the thermal lifetimes drop significantly [38]. It is thus crucial to take into account the asymmetric nature of the imine bond and the steric hindrance of the substituents in the design of these photoswitches. For a detailed analysis of the structure–property relationship of these compounds we
- be synthesised through oxidation of aminoheteroarenes 12 (Scheme 4A) or reduction of nitroheteroarenes 13 (B). Bayer–Mills coupling (Scheme 4C) is suitable for both symmetric and asymmetric targets, usually in acidic conditions. Basic conditions [14] are more effective with very electron-poor
- aromatic amines. Another strategy for both symmetric and asymmetric targets is the azo coupling of a diazonium salt 15 (Scheme 5A) with a nucleophile, which can be a (hetero)aromatic 16 [29] (B), a lithiated ring 19 [39] (C), or a precursor 20a,b [29][32][40] (D). In case of more than one reactive position
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