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Search for "intermolecular" in Full Text gives 774 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis
- Lihua Wei,
- Rui Yang,
- Zhifeng Shi and
- Zhiqiang Ma
Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151
- with 99% ee. The TBS protection was crucial to prevent the potential racemization by intramolecular transesterification. Ester 79 was then prepared from 78 in eight steps. To complete the dimerization, fragments 80 and 81 were independently prepared from 79. An intermolecular Suzuki–Miyaura coupling
- the cyclohexanone ring into 120, and the resulting hydroxy group was protected to give ketone 121. The γ-lactam moiety of compound 122 was then constructed in subsequent 12 steps. SmI2-mediated intermolecular Reformatsky-type reaction with aldehyde 123 yielded compound 124. Finally, salinosporamide A
Graphical Abstract
Scheme 1: General mechanism of a lipase-catalyzed esterification.
Scheme 2: Shishido’s synthesis of (−)-xanthorrhizol (4) and (+)-heliannuol D (8).
Scheme 3: Shishido’s synthesis of a) (−)-heliannuol A (15) and b) heliannuol G (20) and heliannuol H (21).
Scheme 4: Deska’s synthesis of hyperione A (30) and ent-hyperione B (31).
Scheme 5: Huang’s synthesis of (+)-brazilin (37).
Scheme 6: Shishido’s synthesis of (−)-heliannuol D (42) and (+)-heliannuol A (43).
Scheme 7: Chênevert’s synthesis of (S)-α-tocotrienol (49).
Scheme 8: Kita’s synthesis of monoester 53.
Scheme 9: Kita’s synthesis of fredericamycin A (60).
Scheme 10: Takabe’s synthesis of (E)-3,7-dimethyl-2-octene-1,8-diol (64).
Scheme 11: Takabe’s synthesis of (18S)-variabilin (70).
Scheme 12: Kawasaki’s synthesis of (S)-Rosaphen (74) and (R)-Rosaphen (75).
Scheme 13: Tokuyama’s synthesis of a) (−)-petrosin (84) and b) (+)-petrosin (86).
Scheme 14: Fukuyama’s synthesis of leustroducsin B (96).
Scheme 15: Nanda’s synthesis of a) fragment 100, b) fragment 106 and c) (−)-rasfonin (109).
Scheme 16: Davies’ synthesis of (+)-pilocarpine (115) and (+)-isopilocarpine (116).
Scheme 17: Ōmura’s synthesis of salinosporamide A (125).
Scheme 18: Kang’s synthesis of ʟ-cladinose (124) and its derivative.
Scheme 19: Kang’s preparation of fragment 139.
Scheme 20: Kang’s synthesis of azithromycin (149).
Scheme 21: Kang’s synthesis of (−)-dysiherbaine (156).
Scheme 22: Kang’s synthesis of (−)-kaitocephalin (166).
Scheme 23: Kang’s synthesis of laidlomycin (180).
Scheme 24: Snyder’s synthesis of arboridinine (190).
Scheme 25: Ma’s synthesis of (+)-alstrostine G (203).
Scheme 26: Trost’s synthesis of (−)-18-epi-peloruside A (215).
Scheme 27: Lindel’s synthesis of (–)-dihydroraputindole (223).
Scheme 28: Iwata’s synthesis of a) (−)-talaromycin B (232) and b) (+)-talaromycin A (235).
Scheme 29: Cook’s synthesis of a) (−)-vincamajinine (240) and b) (−)-11-methoxy-17-epivincamajine (245).
Scheme 30: Cook’s synthesis of (+)-dehydrovoachalotine (249) and voachalotine (250).
Scheme 31: Cook’s synthesis of a) (−)-12-methoxy-Nb-methylvoachalotine (257) and b) (+)-polyneuridine, macusin...
Scheme 32: Trauner’s synthesis of stephadiamine (273).
Scheme 33: Garg’s synthesis of (–)-ψ-akuammigine (285).
Scheme 34: Ding’s synthesis of (+)-18-benzoyldavisinol (293) and (+)-davisinol (294).
Rhodium-catalysed connective synthesis of diverse reactive probes bearing S(VI) electrophilic warheads
- Scott Rice,
- Julian Chesti,
- William R. T. Mosedale,
- Megan H. Wright,
- Stephen P. Marsden,
- Terry K. Smith and
- Adam Nelson
Beilstein J. Org. Chem. 2025, 21, 1924–1931, doi:10.3762/bjoc.21.150
- estimation of the yield of each product (Figure 2, panel B). It was found that many reactions involving alcohol- (e.g., C1–5, C8, C11 and C14) and indole- (e.g., C3, C12 and C15) containing co-substrates yielded intermolecular products, whilst those involving nitrile-containing co-substrates (C9 and 10) and
- the allylic ether C16 did not. It is remarkable that S(VI) electrophiles are tolerated. Eighteen substrate/co-substrate combinations gave, with at least one of the catalysts, an intermolecular product in >10% estimated yield (typically corresponding to >1 mg product). For all but one of these
- reactions, a product with molecular weight consistent with O–H insertion into water was also observed. For these 18 substrate/co-substrate combinations, the reaction with the highest estimated yield was selected for mass-directed purification (Table 2). In total, 23 intermolecular reaction products were
Graphical Abstract
Figure 1: Envisaged connective synthesis of reactive probes 3 bearing S(VI) electrophilic warheads (WH). Dive...
Scheme 1: Synthesis of α-diazoamide substrates D1–5 of general structure 2 bearing S(VI) electrophiles. Panel...
Figure 2: Structures and reactions of co-substrates. Panel A: structures of the 16 selected co-substrates C1–...
Figure 3: Structures and structure elucidation of intermolecular reaction products. The relevant reactivity m...
Preparation of spirocyclic oxindoles by cyclisation of an oxime to a nitrone and dipolar cycloaddition
- Beth L. Ritchie,
- Alexandra Longcake and
- Iain Coldham
Beilstein J. Org. Chem. 2025, 21, 1890–1896, doi:10.3762/bjoc.21.146
- an important class of compounds with significant biological activities. Spirocyclic derivatives are present in a variety of natural products. We describe here the formation of spirooxindoles using an intermolecular nitrone cycloaddition reaction. The nitrone dipole was prepared in situ by cyclisation
- possibility to access the core of this ring system with the nitrone intermediate shown in Scheme 1A. As a model study, we describe here efforts towards an intermolecular variant with the oxindole shown in Scheme 1B; in this case a leaving group X will be displaced by the oxime to give an intermediate nitrone
Graphical Abstract
Figure 1: Representative oxindole alkaloids.
Scheme 1: Proposed synthetic approach.
Scheme 2: Preparation of the aldehyde 4.
Scheme 3: Cycloaddition with N-methylmaleimide.
Figure 2: Orientation for the cycloaddition (left) and the crystal structure of the major stereoisomer 5a (ri...
Scheme 4: Cycloaddition with N-phenylmaleimide.
Scheme 5: Cycloaddition with dimethyl fumarate and dimethyl maleate.
Photoswitches beyond azobenzene: a beginner’s guide
- Michela Marcon,
- Christoph Haag and
- Burkhard König
Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143
- tautomerism is an intermolecular process that depends not only on the choice of aryl rings and substituents but also on concentration, solvent polarity, and the presence of proton sources [5][15]. In conclusion, the choice of aryl rings, substituents, and substitution position are all crucial to determine the
- concentration of the photoswitch in solution: when MeOH or water are present, the lifetimes drop significantly, and particularly at pH 4, as consequence of more favourable intermolecular proton transfer. Calculations show that water molecules bridging between two Z-isomers favour the formation of hydrazone and
Graphical Abstract
Figure 1: Energy diagram of a two-state photoswitch. Figure 1 was redrawn from [2].
Figure 2: Example of the absorption spectra of the isomers of a photoswitch with most efficient irradiation w...
Scheme 1: Photoswitch classes described in this review.
Figure 3: Azoheteroarenes.
Scheme 2: E–Z Isomerisation (top) and mechanisms of thermal Z–E isomerisation (bottom).
Scheme 3: Rotation mechanism favoured by the electron displacement in push–pull systems. Selected examples of...
Figure 4: A) T-shaped and twisted Z-isomers determine the thermal stability and the Z–E-PSS (selected example...
Figure 5: Effect of di-ortho-substitution on thermal half-life and PSS.
Figure 6: Selected thermal lifetimes of azoindoles in different solvents and concentrations. aConcentration o...
Figure 7: Aryliminopyrazoles: N-pyrazoles (top) and N-phenyl (bottom).
Scheme 4: Synthesis of symmetrical heteroarenes through oxidation (A), reduction (B), and the Bayer–Mills rea...
Scheme 5: Synthesis of diazonium salt (A); different strategies of azo-coupling: with a nucleophilic ring (B)...
Scheme 6: Synthesis of arylazothiazoles 25 (A) and heteroaryltriazoles 28 (B).
Scheme 7: Synthesis of heteroarylimines 31a,b [36-38].
Figure 8: Push–pull non-ionic azo dye developed by Velasco and co-workers [45].
Scheme 8: Azopyridine reported by Herges and co-workers [46].
Scheme 9: Photoinduced phase transitioning azobispyrazoles [47].
Figure 9: Diazocines.
Scheme 10: Isomers, conformers and enantiomers of diazocine.
Scheme 11: Partial overlap of the ππ* band with electron-donating substituents and effect on the PSS. Scheme 11 was ada...
Figure 10: Main properties of diazocines with different bridges. aMeasured in n-hexane [56]. bMeasured in THF. cMe...
Scheme 12: Synthesis of symmetric diazocines.
Scheme 13: Synthesis of asymmetric diazocines.
Scheme 14: Synthesis of O- and S-heterodiazocines.
Scheme 15: Synthesis of N-heterodiazocines.
Scheme 16: Puromycin diazocine photoswitch [60].
Figure 11: Indigoids.
Figure 12: The main representatives of the indigoid photoswitch class.
Scheme 17: Deactivation process that prevents Z-isomerisation of indigo.
Figure 13: Stable Z-indigo derivative synthesised by Wyman and Zenhäusern [67].
Figure 14: Selected examples of indigos with aliphatic and aromatic substituents [68]. Dashed box: proposed π–π in...
Scheme 18: Resonance structures of indigo and thioindigo involving the phenyl ring.
Scheme 19: Possible deactivation mechanism for 4,4'-dihydroxythioindigo [76].
Scheme 20: Effect of different heteroaryl rings on the stability and the photophysical properties of hemiindig...
Figure 15: Thermal half-lives of red-shifted hemithioindigos in toluene [79]. aMeasured in toluene-d8.
Scheme 21: Structures of pyrrole [81] and imidazole hemithioindigo [64].
Figure 16: Examples of fully substituted double bond hemithioindigo (left), oxidised hemithioindigos (centre),...
Scheme 22: Structure of iminothioindoxyl 72 (top) and acylated phenyliminoindolinone photoswitch 73 (bottom). ...
Scheme 23: (top) Transition states of iminothioindoxyl 72. The planar transition state is associated with a lo...
Scheme 24: Baeyer–Drewsen synthesis of indigo (top) and N-functionalisation strategies (bottom).
Scheme 25: Synthesis of hemiindigo.
Scheme 26: Synthesis of hemithioindigo and iminothioindoxyl.
Scheme 27: Synthesis of double-bond-substituted hemithioindigos.
Scheme 28: Synthesis of phenyliminoindolinone.
Scheme 29: Hemithioindigo molecular motor [85].
Figure 17: Arylhydrazones.
Scheme 30: Switching of arylhydrazones. Note: The definitions of stator and rotor are arbitrary.
Scheme 31: Photo- and acidochromism of pyridine-based phenylhydrazones.
Scheme 32: A) E–Z thermal inversion of a thermally stable push–pull hydrazone [109]. B) Rotation mechanism favoured...
Scheme 33: Effect of planarisation on the half-life.
Scheme 34: The longest thermally stable hydrazone switches reported so far (left). Modulation of thermal half-...
Figure 18: Dependency of t1/2 on concentration and hypothesised aggregation-induced isomerisation.
Figure 19: Structure–property relationship of acylhydrazones.
Scheme 35: Synthesis of arylhydrazones.
Scheme 36: Synthesis of acylhydrazones.
Scheme 37: Photoswitchable fluorophore by Aprahamian et al. [115].
Scheme 38: The four-state photoswitch synthesised by the Cigáň group [116].
Figure 20: Diarylethenes.
Scheme 39: Isomerisation and oxidation pathway of E-stilbene to phenanthrene.
Scheme 40: Strategies adapted to avoid E–Z isomerisation and oxidation.
Scheme 41: Molecular orbitals and mechanism of electrocyclisation for a 6π system.
Figure 21: Aromatic stabilisation energy correlated with the thermal stability of the diarylethenes [127,129].
Figure 22: Half-lives of diarylethenes with increasing electron-withdrawing groups [128,129].
Scheme 42: Photochemical degradation pathway promoted by electron-donating groups [130].
Figure 23: The diarylethenes studied by Hanazawa et al. [134]. Increased rigidity leads to bathochromic shift.
Scheme 43: The dithienylethene synthesised by Nakatani's group [135].
Scheme 44: Synthesis of perfluoroalkylated diarylethenes.
Scheme 45: Synthesis of 139 and 142 via McMurry coupling.
Scheme 46: Synthesis of symmetrical derivatives 145 via Suzuki–Miyaura coupling.
Scheme 47: Synthesis of acyclic 148, malonic anhydride 149, and maleimide derivatives 154.
Figure 24: Gramicidin S (top left) and two of the modified diarylethene derivatives: first generation (bottom ...
Scheme 48: Pyridoxal 5'-phosphate and its reaction with an amino acid (top). The analogous dithienylethene der...
Figure 25: Fulgides.
Scheme 49: The three isomers of fulgides.
Scheme 50: Thermal and photochemical side products of unsubstituted fulgide [150].
Figure 26: Maximum absorption λc of the closed isomer compared with the nature of the aromatic ring and the su...
Scheme 51: Possible rearrangement of the excited state of 5-dimethylaminoindolylfulgide [153].
Figure 27: Quantum yields of ring closure (ΦE→C) and E–Z isomerisation (ΦE→Z) correlated with the increasing s...
Scheme 52: Active (Eα) and inactive (Eβ) conformers (left) and the bicyclic sterically blocked fulgide 169 (ri...
Scheme 53: Quantum yield of ring-opening (ΦC→E) and E–Z isomerisation (ΦE→Z) for different substitution patter...
Scheme 54: Stobbe condensation pathway for the synthesis of fulgides 179, fulgimides 181 and fulgenates 178.
Scheme 55: Alternative synthesis of fulgides through Pd-catalysed carbonylation.
Scheme 56: Optimised synthesis of fulgimides [166].
Scheme 57: Photoswitchable FRET with a fulgimide photoswitch [167].
Scheme 58: Three-state fulgimide strategy by Slanina's group.
Figure 28: Spiropyrans.
Scheme 59: Photochemical (left) and thermal (right) ring-opening mechanisms for an exemplary spiropyran with a...
Figure 29: Eight possible isomers of the open merocyanine according to the E/Z configurations of the bonds hig...
Scheme 60: pH-Controlled photoisomerisation between the closed spiropyran 191-SP and the open E-merocyanine 19...
Scheme 61: Behaviour of spiropyran in water buffer according to Andréasson and co-workers [180]. 192-SP in an aqueo...
Scheme 62: (left box) Proposed mechanism of basic hydrolysis of MC [184]. (right box) Introduction of electron-dona...
Scheme 63: Photochemical interconversion of naphthopyran 194 (top) and spirooxazine 195 (bottom) photoswitches...
Scheme 64: Synthesis of spiropyrans and spirooxazines 198 and the dicondensation by-product 199.
Scheme 65: Alternative synthesis of spiropyrans and spirooxazines with indolenylium salt 200.
Scheme 66: Synthesis of 4’-substituted spiropyrans 203 by condensation of an acylated methylene indoline 201 w...
Scheme 67: Synthesis of spironaphthopyrans 210 by acid-catalysed condensation of naphthols and diarylpropargyl...
Scheme 68: Photoswitchable surface wettability [194].
Figure 30: Some guiding principles for the choice of the most suitable photoswitch. Note that this guide is ve...
Research progress on calixarene/pillararene-based controlled drug release systems
- Liu-Huan Yi,
- Jian Qin,
- Si-Ran Lu,
- Liu-Pan Yang,
- Li-Li Wang and
- Huan Yao
Beilstein J. Org. Chem. 2025, 21, 1757–1785, doi:10.3762/bjoc.21.139
- ) [103]. CA4-Man3-NPs achieve efficient targeted drug delivery through a unique self-assembly mechanism. This system leverages the unique polymeric characteristics of CA4, which reduces the critical aggregation concentration and enhance intermolecular orderliness to form structurally stable nanocarriers
Graphical Abstract
Figure 1: Schematic diagram of drug-controlled release mechanisms based on aromatic macrocycles.
Figure 2: Chemical structure of a) calix[n]arene (m = 1,3,5), and b) pillar[n]arene (m = 1,2,3).
Figure 3: Changes in pH conditions cause the release of drugs from CA8 host–guest complexes [101]. Figure 3 was adapted wi...
Figure 4: The illustration of the pH-mediated 1:1 complex formation between the host and guest molecules in a...
Figure 5: Illustration of the pH-responsive self-assembly of mannose-modified CA4 into micelles and the subse...
Figure 6: Illustration of the assembly of supramolecular prodrug nanoparticles from WP6 and DOX-derived prodr...
Figure 7: Illustration of the formation of supramolecular vesicles and their pH-dependent drug release [93]. Figure 7 was...
Figure 8: Schematic illustration of the application of the multifunctional nanoplatform CyCA@POPD in combined...
Figure 9: Illustration of the photolysis of an amphiphilic assembly via CA-induced aggregation [114]. Figure 9 was reprint...
Figure 10: Schematic illustration of drug release controlled by the photo-responsive macroscopic switch based ...
Figure 11: Schematic illustration of the formation process of Azo-SMX and its photoisomerization reaction unde...
Figure 12: Schematic illustration of the enzyme-responsive behavior of supramolecular polymers [95]. Figure 12 was used wit...
Figure 13: Schematic illustration of the amphiphilic assembly of SC4A and its enzyme-responsive applications [119]. ...
Figure 14: Stimuli-responsive nanovalves based on MSNs and choline-SC4A[2]pseudorotaxanes, MSN-C1 with ester-l...
Figure 15: A schematic diagram showing the construction of a supramolecular system by host–guest interaction b...
Figure 16: A schematic diagram showing the formation of the host–guest complex DOX@Biotin-SAC4A by biotin modi...
Figure 17: A schematic diagram showing the self-assembly of CA4 into a hypoxia-responsive peptide hydrogel, wh...
Figure 18: Schematic illustration of the formation process of Lip@GluAC4A and the release of Lip under hypoxic...
Figure 19: Schematic illustration of the construction of a supramolecular vesicle based on the host–guest comp...
Figure 20: Schematic illustration of WP6 self-assembly at pH > 7, and the stimulus-responsive drug release beh...
Figure 21: Schematic illustration of the formation of supramolecular vesicles based on the WP5⊃G super-amphiph...
Figure 22: Schematic illustrations of the host–guest recognition of QAP5⊃SXD, the formation of the nanoparticl...
Figure 23: Schematic illustration of the activation of T-SRNs by acid, alkali, or Zn2+ stimuli to regulate the...
Figure 24: Illustration of the triggered release of BH from CP[5]A@MSNs-Q NPs in response to a drop in pH or a...
Figure 25: Illustration of the supramolecular amphiphiles TPENCn@1 (n = 6 and 12) self-assembling with disulfi...
Unique halogen–π association detected in single crystals of C–N atropisomeric N-(2-halophenyl)quinolin-2-one derivatives and the thione analogue
- Mai Uchibori,
- Nanami Murate,
- Kanako Shima,
- Tatsunori Sakagami,
- Ko Kanehisa,
- Gary James Richards,
- Akiko Hori and
- Osamu Kitagawa
Beilstein J. Org. Chem. 2025, 21, 1748–1756, doi:10.3762/bjoc.21.138
- N-(2-bromo- or 2-chlorophenyl)quinolin-2-ones, homochiral layered polymers, which consist of (P)- or (M)-atropisomers, were formed through intermolecular halogen–π association. The halogen–π association in the racemates is due to a halogen bond (C–X···π) between a σ-hole on the halogen atom and a π
- C–N atropisomers and their structural properties for over 25 years [16][17]. As a part of the C–N atropisomeric chemistry, we succeeded in the asymmetric synthesis of mebroqualone (I) and the thione analogue II [18][19]. In the course of this study, it was found that intermolecular association in
- through a σ-type intermolecular halogen bonding (C–Br···O) between the ortho-bromine atom and the carbonyl oxygen. The formation of similar heterochiral polymers through a σ-type intermolecular halogen bond (C–Br···S) was also found in crystals of the thio-analogue rac-II. On the other hand, in the
Graphical Abstract
Figure 1: Various C–N atropisomeric compounds and their intermolecular interactions in single crystals.
Scheme 1: Synthesis of N-(2-halophenyl)quinolin-2-ones 1a,b and quinoline-2-thione 2a.
Figure 2: Intramolecular associations detected in crystals of rac-1a and rac-1b.
Figure 3: Intramolecular association detected in the crystals of (P)-1a and (P)-1b.
Figure 4: Angles (θ, α) and distances (d) in racemate rac-1a,b and (P)-1a,b.
Figure 5: Crystal structure of racemic quinoline-2-thione rac-2a.
Thermodynamics and polarity-driven properties of fluorinated cyclopropanes
- Matheus P. Freitas
Beilstein J. Org. Chem. 2025, 21, 1742–1747, doi:10.3762/bjoc.21.137
- providing the greatest stability due to strong anomeric-like interactions that enhance electron delocalization. Notably, the all-cis-1,2,3-trifluorocyclopropane (1.2.3-c.c.) was identified as the most polar compound, with its Janus-like electrostatic potential enabling unique intermolecular interactions
Graphical Abstract
Figure 1: Structures of fluorinated cyclopropanes evaluated in this study through quantum chemical methods.
Figure 2: (a) Electrostatic potential map of 1.2.3-c.c., highlighting the negative region (top side) and posi...
Figure 3: Calculated complexes of 1.2.3-c.c. with Na+ (top) and Cl− (bottom).
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
- selectivity in glycosylations with various types of nucleophiles [67][68]. This remarkable stereoselectivity has been attributed to intermolecular hydrogen bonding, which forms a transient tether between the glycosyl donor and acceptor, thereby guiding the reaction towards a preferred stereochemical outcome
Graphical Abstract
Scheme 1: Application of chloride-, bromide-, and trichloroacetimidate donors in 1,1'-coupling reactions towa...
Scheme 2: Application of trichloroacetimidates as donors in 1,1'-β,α coupling reactions and the use of 1,2-or...
Scheme 3: The β-anomeric configuration in the lactol acceptors can be trapped and fixed within the five-membe...
Scheme 4: Diarylborinic acid-promoted β,α-1,1' glycosylation.
Scheme 5: The anomeric configuration in the lactol acceptor can be trapped in the form of a TMS-glycoside.
Scheme 6: The anomeric configuration in the lactol acceptor can be trapped in form of a 1-O-TMS-glycoside tha...
Scheme 7: Influence of remote protecting groups on the stereoselectivity and efficiency of 1,1'-β,α bond form...
Scheme 8: Synthesis of non-symmetrically fully orthogonally protected β,α-1,1' diglucosamines.
Scheme 9: Synthesis of non-symmetric β,β-1,1'-linked disaccharides.
Scheme 10: Synthesis of non-symmetric, fully orthogonally protected β,β-1,1'-diglucosamines.
Scheme 11: Synthesis of α,α-1,1'-disaccharides.
Scheme 12: Synthesis of α,α-1,1'-thiodisacchrides.
Scheme 13: Synthesis of partially desymmetrized α,α-1,1'-linked disaccharides.
Scheme 14: Synthesis of non-symmetric orthogonally protected α,α-1,1'-linked disaccharides involving an aminos...
Synthesis of optically active folded cyclic dimers and trimers
- Ena Kumamoto,
- Kana Ogawa,
- Kazunori Okamoto and
- Yasuhiro Morisaki
Beilstein J. Org. Chem. 2025, 21, 1603–1612, doi:10.3762/bjoc.21.124
- same absolute configuration. The |glum| value of 7 was 0.4 × 10−3 (Figure S18A, Supporting Information File 1), which was lower than that of 6. In the case of the film states of 6 and 7, low PL brightness and intermolecular random orientation of fluorophores resulted in noisy CPL signals. The CD
Graphical Abstract
Scheme 1: Synthesis of cyclic dimer (Sp)-6 and trimer (Sp)-7.
Figure 1: UV–vis and PL spectra of (Sp)-6 and (Sp)-7 in CHCl3 (1.0 × 10−5 M). Excitation wavelength 370 nm an...
Figure 2: (A) UV, CD, PL, and CPL spectra of (Sp)- and (Rp)-6 in CHCl3 (1.0 × 10−5 M). (B) UV, CD, PL, and CP...
Figure 3: (A) CD spectrum of (Sp)-6 in CHCl3 (1.0 × 10−5 M), and the plot of the calculated rotatory strength...
Figure 4: Molecular orbitals and simulated CPL profiles in the S1 states of (A) (Sp)-6 and (B) (Sp)-7 (TD-MN1...
3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles
- Julia I. Pavlenko,
- Pavel A. Sakharov,
- Anastasiya V. Agafonova,
- Derenik A. Isadzhanyan,
- Alexander F. Khlebnikov and
- Mikhail S. Novikov
Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123
- reactions of intermolecular annulation of a variety of non-aromatic five- [4][5][6] and six-membered carbo- and heterocycles [7][8][9] with azirines, which occur under transition metal catalysis or photocatalysis. Annulation of the pyrrole ring to an aromatic system is limited to reactions of functionalized
- formation of the C–C bond between the rings of the reacting molecules occurs in the coordination metal sphere as an intra-, rather than intermolecular, process. The formation of compound 17, the product of oxidative dimerization of indole-based enol 15, in the second reaction also points to different
Graphical Abstract
Scheme 1: Synthesis of fused pyrroles and azoles by [3 + 2] annulation reactions of azirines.
Scheme 2: Synthesis of benzo[4,5]thieno[3,2-b]pyrroles 3.
Scheme 3: Plausible mechanism for the formation of compounds 3.
Scheme 4: Post-modifications of 1H-benzo[4,5]thieno[3,2-b]pyrrole (3b).
Scheme 5: Synthesis of pyrrolo[3,2-b]indole 10.
Scheme 6: IPrCuCl-catalyzed reactions of indoles 9b,c with azirine 2a.
Scheme 7: Ni(II)- and Cu(I)-catalyzed reactions of indole 15 with azirine 2a.
Highly distinguishable isomeric states of a tripodal arylazopyrazole derivative on graphite through electron/hole-induced switching at ambient conditions
- Himani Malik,
- Sudha Devi,
- Debapriya Gupta,
- Ankit Kumar Gaur,
- Sugumar Venkataramani and
- Thiruvancheril G. Gopakumar
Beilstein J. Org. Chem. 2025, 21, 1496–1507, doi:10.3762/bjoc.21.112
- (≈120°), the angle between the vectors. The intermolecular distance obtained from STM corresponds to the lateral length of the EEE isomer (F to F distance is 22.06 Å). Thus, we conclude that the adlayer is formed by the energetically most favorable EEE isomer. This is also consistent with the NMR data
- is not a surprise [10][36]. Therefore, it is summarized that the typical intermolecular interactions are of van der Waals type and interactions dominantly driven by steric packing. We note that the STM experiments reveal only a hexagonal type of arrangement of molecules, as shown in Figure 3
Graphical Abstract
Figure 1: Top panel: Chemical structures of EEE, and ZZZ isomers of (FNAAP). Lower panel: Geometry-optimized ...
Figure 2: AFM phase images (a, b and c) of ultra-thin films of FNAAP deposited from ethanolic solution on HOP...
Figure 3: Constant current STM topographs (300 pA, 0.3 V) of the FNAAP adlayer on HOPG (a, b) deposited from ...
Figure 4: (a) Current versus sample voltage (I–V) recorded on a single FNAAP within the assembly. The I–V mea...
Figure 5: (a) Current versus time (time trace) at selected voltage intervals acquired on the adlayer of FNAAP...
Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications
- Meng Qiu,
- Jing Du,
- Nai-Te Yao,
- Xin-Yue Wang and
- Han-Yuan Gong
Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106
- versatile scaffolds for chiral optoelectronic applications. The incorporation of nitrogen enables precise modulation of electronic structures, redox characteristics, and intermolecular interactions, thereby enhancing performance in circularly polarized luminescence (CPL), thermally activated delayed
- structures, enhance solubility, and expand functional diversity [6]. Substituting carbon atoms with electron-deficient nitrogen atoms introduces new opportunities to fine-tune redox potentials, charge-transport behavior, and intermolecular interactions [7]. These modifications have proven especially valuable
- , attributed to intermolecular hydrogen bonding with solvent molecules. With increasing helical length, both the λabs and λem exhibit progressive bathochromic shifts, while the ФF values systematically decline, without clear saturation within the investigated range. Chiroptical measurements of the N-butylated
Tautomerism and switching in 7-hydroxy-8-(azophenyl)quinoline and similar compounds
- Lidia Zaharieva,
- Vera Deneva,
- Fadhil S. Kamounah,
- Nikolay Vassilev,
- Ivan Angelov,
- Michael Pittelkow and
- Liudmil Antonov
Beilstein J. Org. Chem. 2025, 21, 1404–1421, doi:10.3762/bjoc.21.105
- reasons are different. While in acetonitrile this is the effect of the increased polarity of the solvent, leading to stabilization of the more polar keto tautomers, in the non-polar chloroform it is caused by its proton-donative nature (formation of a stabilizing intermolecular hydrogen bonding with the C
Graphical Abstract
Scheme 1: Investigated compounds.
Scheme 2: Long-range PT in the studied compounds along with undesired processes of E/Z isomerization. The ind...
Figure 1: Simulated absorption spectra of the tautomers of 1 in toluene. The spectra in acetonitrile are show...
Figure 2: Normalized absorption spectra of 1.
Figure 3: Absorption spectra of 1 in acetonitrile with stepwise addition of water.
Figure 4: VT 1H NMR spectra of compound 1 in acetonitrile-d3.
Figure 5: Changes in the absorption spectrum of 2 in acetonitrile upon addition of trifluoroacetic acid (TFA)...
Figure 6: Ground (M06-2X/TZVP) and excited (CAM-B3LYP/TZVP) state potential energy surface of compound 1 in t...
Figure 7: Changes of the absorbance of compound 1 at 465 nm in toluene upon turning on and off the irradiatio...
Figure 8: a) Change of ΔE(K-E) in kcal/mol as a function of the substitution on different positions (2–6) in ...
Scheme 3: Perspective switching compounds, generated by the computational quantum chemistry calculations.
Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles
- Vladimir G. Ilkin,
- Pavel S. Silaichev,
- Valeriy O. Filimonov,
- Tetyana V. Beryozkina,
- Margarita D. Likhacheva,
- Pavel A. Slepukhin,
- Wim Dehaen and
- Vasiliy A. Bakulev
Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104
- involved in the formation of a weak intermolecular hydrogen bond of the C‒H···N≡C type with distances H(3)···N(3) 2.53(3) Å, C(3)···N(3) 3.436(4) Å and angle C(3)H(3)N(3) 157(2)° (symmetry transformation [1−x, 1−y, 1−z]). Conclusion Thus, we found that thioamides of acrylic acid easily interact with
Graphical Abstract
Figure 1: Representatives of biologically active 1,2-thiazoles.
Scheme 1: Synthesis of 2,5-dihydro-1,2-thiazoles.
Scheme 2: Synthesis of 2,3-dihydro-N-sulfonyl-1,2-thiazoles 3. Conditions: aMethod A: thioamide 1 (1.0 equiv)...
Figure 2: Compound 3aa in thermal ellipsoids 50% probability.
Oxetanes: formation, reactivity and total syntheses of natural products
- Peter Gabko,
- Martin Kalník and
- Maroš Bella
Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101
- greatly exploited in the past [34] and new protocols are still being developed and reported. These reactions can be divided into intramolecular and intermolecular processes and they usually rely on oxygen- or nitrogen-based nucleophiles, but ring openings involving hydrides and soft carbon nucleophiles
- –2021, Kuduk and co-workers published three different tandem, one-pot methodologies towards complex polycyclic heterocycles [100][101][102]. All of them are two-step reactions consisting of an intermolecular coupling followed by an intramolecular, base-induced oxetane opening (Scheme 48). The first one
Graphical Abstract
Figure 1: Bond lengths and bond angles in oxetane at 140 K [2].
Figure 2: Analogy of 3-substituted oxetanes to carbonyl and gem-dimethyl groups [12].
Figure 3: Use of oxetanes in drug design – selected examples.
Figure 4: Examples of oxetane-containing natural products.
Scheme 1: Synthetic strategies towards construction of the oxetane ring.
Scheme 2: Overview of intramolecular Williamson etherification and competing Grob fragmentation.
Scheme 3: Synthesis of spiro-oxetanes via 1,4-C–H insertion and Williamson etherification.
Scheme 4: Use of phenyl vinyl selenone in the synthesis of spirooxindole oxetanes.
Scheme 5: Synthesis of bicyclic 3,5-anhydrofuranoses via double epoxide opening/etherification.
Scheme 6: Preparation of spirooxetanes by cycloisomerisation via MHAT/RPC.
Scheme 7: Oxetane synthesis via alcohol C–H functionalisation.
Scheme 8: Access to oxetanes 38 from α-acetyloxy iodides.
Scheme 9: The kilogram-scale synthesis of oxetane intermediate 41.
Scheme 10: Overview of the intramolecular opening of 3-membered rings.
Scheme 11: Synthesis of 4,7-dioxatricyclo[3.2.1.03,6]octane skeletons.
Scheme 12: Silicon-directed electrophilic cyclisation of homoallylic alcohols.
Scheme 13: Hydrosilylation–iodocyclisation of homopropargylic alcohols.
Scheme 14: Cu-catalysed intramolecular O-vinylation of γ-bromohomoallylic alcohols.
Scheme 15: Cu-catalysed intramolecular cross-coupling of hydroxyvinylstannanes.
Scheme 16: Isomerisation of oxiranyl ethers containing weakly carbanion-stabilising groups.
Scheme 17: Cyclisation of diethyl haloalkoxymalonates.
Scheme 18: Synthesis of oxetanes through a 1,5-HAT/radical recombination sequence.
Scheme 19: General approach to oxetanes via [2 + 2] cycloadditions.
Scheme 20: Synthesis of tricyclic 4:4:4 oxetanes through a photochemical triple cascade reaction.
Scheme 21: Iridium-catalysed Paternò–Büchi reaction between α-ketoesters and simple alkenes.
Scheme 22: Three-step synthesis of spirocyclic oxetanes 83 via Paternò–Büchi reaction, nucleophilic ring openi...
Scheme 23: Enantioselective Paternò–Büchi reaction catalysed by a chiral iridium photocatalyst.
Scheme 24: Synthesis of polysubstituted oxetanes 92 via Cu(II)-mediated formal [2 + 2] cycloadditions.
Scheme 25: Synthesis of alkylideneoxetanes via NHC- and DBU-mediated formal [2 + 2] cycloadditions.
Scheme 26: Use of sulphur-stabilised carbanions in ring expansions.
Scheme 27: Synthesis of α,α-difluoro(arylthio)methyl oxetanes.
Scheme 28: Ring expansion in an industrial synthesis of PF-06878031.
Scheme 29: Ring contraction of triflated 2-hydroxy-γ-lactones.
Scheme 30: Ring contraction in an industrial synthesis of PF-06878031.
Scheme 31: Photochemical ring contraction of 2,5-dihydrofurans by aryldiazoacetic acid esters.
Scheme 32: Synthesis of 3-oxetanones via O-H insertion of carbenes.
Scheme 33: Synthesis of phosphonate oxetanones via gold-mediated alkyne oxidation/O–H insertion.
Scheme 34: Syntheses and common derivatisations of 3-oxetanone.
Scheme 35: SN1 substitution of 3-aryloxetan-3-ols by thiols and alcohols.
Scheme 36: Fe–Ni dual-catalytic olefin hydroarylation towards 3-alkyl-3-(hetero)aryloxetanes.
Scheme 37: Synthesis of 3-aryloxetan-3-carboxylic acids.
Scheme 38: Decarboxylative alkylation of 3-aryloxetan-3-carboxylic acids.
Scheme 39: Synthesis of 3-amino-3-aryloxetanes via photoredox/nickel cross-coupling catalysis.
Scheme 40: Intermolecular cross-selective [2 + 2] photocycloaddition towards spirooxetanes.
Scheme 41: Synthesis of 3-aryl-3-aminooxetanes via defluorosulphonylative coupling.
Scheme 42: Two-step synthesis of amide bioisosteres via benzotriazolyl Mannich adducts 170.
Scheme 43: Functionalisation of oxetanyl trichloroacetimidates 172.
Scheme 44: Synthesis of oxetane-amino esters 176.
Scheme 45: Tandem Friedel–Crafts alkylation/intramolecular ring opening of 3-aryloxetan-3-ols.
Scheme 46: Synthesis of polysubstituted furans and pyrroles.
Scheme 47: Synthesis of oxazolines and bisoxazolines.
Scheme 48: Tandem, one-pot syntheses of various polycyclic heterocycles.
Scheme 49: Synthesis of 1,2-dihydroquinolines via skeletal reorganisation of oxetanes.
Scheme 50: Synthesis of benzoindolines and 2,3-dihydrobenzofurans and their derivatisations.
Scheme 51: Synthesis of polysubstituted 1,4-dioxanes.
Scheme 52: Preparation of various lactones via ring opening of oxetane-carboxylic acids 219.
Scheme 53: Tsuji-Trost allylation/ring opening of 3-aminooxetanes.
Scheme 54: Arylative skeletal rearrangement of 3-vinyloxetan-3-ols to 2,5-dihydrofurans.
Scheme 55: Reductive opening of oxetanes using catalytic Mg–H species.
Scheme 56: Opening of oxetanes by silyl ketene acetals.
Scheme 57: Rhodium-catalysed hydroacylation of oxetanes.
Scheme 58: Generation of radicals from oxetanes mediated by a vitamin B12-derived cobalt catalyst.
Scheme 59: Reductive opening of oxetanes by B–Si frustrated Lewis pairs.
Scheme 60: Zirconocene-mediated reductive opening of oxetanes.
Scheme 61: Enantioselective syntheses of small and medium-size rings using chiral phosphoric acids.
Scheme 62: Asymmetric synthesis of 2,3-dihydrobenzo[b]oxepines catalysed by a chiral scandium complex.
Scheme 63: Enantioselective synthesis of 1,3-bromohydrins under a chiral squaramide catalysis.
Scheme 64: Enantioselective opening of 2-aryl-2-ethynyloxetanes by anilines.
Scheme 65: Ru-catalysed insertion of diazocarbonyls into oxetanes.
Scheme 66: Ring expansion of oxetanes by stabilised carbenes generated under blue light irradiation.
Scheme 67: Expansion of oxetanes via nickel-catalysed insertion of alkynyltrifluoroborates.
Scheme 68: Nickel-catalysed expansion of oxetanes into ε-caprolactones.
Scheme 69: Expansion of oxetanes via cobalt-catalysed carbonyl insertion.
Scheme 70: Gold-catalysed intramolecular 1,1-carboalkoxylation of oxetane-ynamides.
Scheme 71: Expansion of oxetanes by stabilised sulphoxonium ylides.
Scheme 72: Cu-catalysed ring expansion of 2-vinyloxetanes by diazoesters.
Scheme 73: Total synthesis of (+)-oxetin.
Scheme 74: Total synthesis of racemic oxetanocin A.
Scheme 75: Total synthesis of (−)-merrilactone A.
Scheme 76: Total synthesis of (+)-dictyoxetane.
Scheme 77: Total synthesis of ent-dichrocephone B.
Scheme 78: Total synthesis of (−)-mitrephorone A.
Scheme 79: Total synthesis of (−)-taxol.
Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer
- Hao-Sen Wang,
- Lin Li,
- Xin Chen,
- Jian-Li Wu,
- Kai Sun,
- Xiao-Lan Chen,
- Ling-Bo Qu and
- Bing Yu
Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100
- of amidyl radicals as HAT reagents, with a particular emphasis on their role in the intermolecular HAT process. We highlight key developments, mechanistic insights, and emerging strategies that harness the unique reactivity of amidyl radicals in the selective functionalization of a variety of
- activation energy modulation during transition state formation. Specifically, donor/acceptor electronic configurations in the substrate could either stabilize or destabilize the transient hybrid state, thereby thermodynamically governing the energy barrier for intermolecular HAT progression. When the partial
- insight in the development of novel methods for amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer. Although, amidyl radicals employed in many reactions as HAT reagents via heating conditions have been summarized in several studies [52][53][54][55][56][57][58]. To advance
Graphical Abstract
Figure 1: (a) BDE of C–H. (b) Direct functionalization of C–H catalyzed by transition-metal. (c) Direct funct...
Figure 2: (a) Amidyl radical-enabled hydrogen atom transfer. (b) Substituent effects to amidyl radical proper...
Figure 3: Representative photocatalysts discussed in this review.
Scheme 1: Alkylation of C(sp3)–H catalyzed by amidyl radical under visible light.
Scheme 2: Direct heteroarylation of C(sp3)–H catalyzed by amidyl radical under visible light.
Scheme 3: Alkylation of C(sp3)–H catalyzed by amidyl radical and metal-free photocatalyst under visible light....
Scheme 4: Alkylation of C(sp3)–H, Si–H, and Ge–H catalyzed by amidyl radical under visible light.
Scheme 5: Direct heteroarylation of C(sp3)–H catalyzed by synergistic promotion of amidyl radical and photoca...
Scheme 6: Direct B–H functionalization of icosahedral carboranes catalyzed by amidyl radical under visible li...
Scheme 7: Nucleophilic amination of C(sp3)–H enabled by amidyl radical under visible light.
Scheme 8: Direct heteroarylation of C(sp3)–H and C(sp3)–H without the presence of strong bases, acids, or oxi...
Scheme 9: Xanthylation of C(sp3)–H addressed by amidyl radical under visible light.
Scheme 10: Xanthylation of C(sp3)–H in polyolefins addressed by amidyl radical under visible light.
Scheme 11: Site-selective C(sp3)–H bromination implemented by amidyl radical under visible light.
Scheme 12: Site-selective chlorination of C(sp3)–H in natural products implemented by amidyl radical under vis...
Scheme 13: Alkylation of C(sp3)–H catalyzed by amidyl radical photocatalyst under visible light.
Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes
- Bartłomiej Pigulski
Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99
- and co-workers [55]. A palladium-catalysed variation of [3 + 2] annulation, accompanied by ring expansion [56], was used for the intermolecular reaction between acenes bearing alkyne substituents 55a–d and di-n-butylacetylene (56). The reaction gave a series of azulene-embedded isomers of linear
Graphical Abstract
Figure 1: a) Stone–Wales (red) and azulene (blue) defects in graphene; b) azulene and its selected resonance ...
Figure 2: Examples of azulene-embedded 2D allotropic forms of carbon: a) phagraphene and b) TPH-graphene.
Scheme 1: Synthesis of non-alternant isomers of pyrene (2 and 6) using dehydrogenation.
Scheme 2: Synthesis of non-alternant isomer 9 of benzo[a]pyrene and 14 of benzo[a]perylene using dehydrogenat...
Scheme 3: Synthesis of azulene-embedded isomers of benzo[a]pyrene (18 and 22) inspired by Ziegler–Hafner azul...
Figure 3: General strategies leading to azulene-embedded nanographenes: a) construction of azulene moiety in ...
Scheme 4: Synthesis of biradical PAHs possessing significant biradical character using oxidation of partially...
Scheme 5: Synthesis of dicyclohepta[ijkl,uvwx]rubicene (29) and its further modifications.
Scheme 6: Synthesis of warped PAHs with one embedded azulene subunit using Scholl-type oxidation.
Scheme 7: Synthesis of warped PAHs with two embedded azulene subunits using Scholl oxidation.
Scheme 8: Synthesis of azulene-embedded PAHs using [3 + 2] annulation accompanied by ring expansion.
Scheme 9: Synthesis of azulene-embedded isomers of linear acenes using [3 + 2] annulation accompanied by ring...
Scheme 10: Synthesis of azulene-embedded PAHs using intramolecular C–H arylation.
Scheme 11: Synthesis of azulene-embedded isomers of acenes using intramolecular C–H arylation.
Scheme 12: Synthesis of azulene-embedded PAHs using intramolecular condensations.
Scheme 13: Synthesis of azulene-embedded PAH 89 using palladium-catalysed [5 + 2] annulation.
Scheme 14: Synthesis of azulene-embedded PAHs using oxidation of substituents around the azulene core.
Scheme 15: Synthesis of azulene-embedded PAHs using the oxidation of reactive positions 1 and 3 of azulene sub...
Scheme 16: Synthesis of azulene-embedded PAHs using intramolecular C–H arylation.
Scheme 17: Synthesis of an azulene-embedded isomer of terylenebisimide using tandem Suzuki coupling and C–H ar...
Scheme 18: Synthesis of azulene embedded PAHs using a bismuth-catalyzed cyclization of alkenes.
Scheme 19: Synthesis of azulene-embedded nanographenes using intramolecular cyclization of alkynes.
Scheme 20: Synthesis of azulene-embedded graphene nanoribbons and azulene-embedded helicenes using annulation ...
Scheme 21: Synthesis of azulene-fused acenes.
Scheme 22: Synthesis of non-alternant isomer of perylene 172 using Yamamoto-type homocoupling.
Scheme 23: Synthesis of N- and BN-nanographenes with embedded azulene unit(s).
Scheme 24: On-surface synthesis of azulene-embedded nanographenes from benzenoid precursors via dehydrogenatio...
Scheme 25: On-surface synthesis of azulene-embedded nanographenes from benzenoid precursors.
Scheme 26: On-surface synthesis of azulene-embedded nanoribbons.
Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents
- Jiangfei Chen,
- Yi-Lin Qu,
- Ming Yuan,
- Xiang-Mei Wu,
- Heng-Pei Jiang,
- Ying Fu and
- Shengrong Guo
Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98
- oxidant and initiator, enabling an efficient intermolecular cascade cyclization process (Scheme 5) [5]. In this strategy, a novel, selective, metal-free synthetic method was introduced for the synthesis of isoxazoline-featured oxindoles through iminoxyl radical-promoted cascade oxyalkylation
- elimination or single-electron oxidation and deprotonation, yielding the final oxindole products 81 and regenerating the Pd(0) catalyst I. In the same year, Zhang’s group developed a novel visible-light-induced palladium-catalyzed intermolecular radical cascade cyclization of N-arylacrylamides with
- for constructing quaternary carbon centers in oxindoles via an N-heterocyclic carbene (NHC)-catalyzed intermolecular Heck-type alkyl radical addition and annulation reaction (Scheme 47) [28]. The reaction proceeds through a redox-neutral mechanism, where the NHC catalyst serves a dual role as both a
Graphical Abstract
Scheme 1: DTBP-mediated oxidative alkylarylation of activated alkenes.
Scheme 2: Iron-catalyzed oxidative 1,2-alkylarylation.
Scheme 3: Possible mechanism for the iron-catalyzed oxidative 1,2-alkylation of activated alkenes.
Scheme 4: A metal-free strategy for synthesizing 3,3-disubstituted oxindoles.
Scheme 5: Iminoxyl radical-promoted cascade oxyalkylation/alkylarylation of alkenes.
Scheme 6: Proposed mechanism for the iminoxyl radical-promoted cascade oxyalkylation/alkylarylation of alkene...
Scheme 7: Bicyclization of 1,n-enynes with alkyl nitriles.
Scheme 8: Possible reaction mechanism for the bicyclization of 1,n-enynes with alkyl nitriles.
Scheme 9: Radical cyclization of N-arylacrylamides with isocyanides.
Scheme 10: Plausible mechanism for the radical cyclization of N-arylacrylamides with isocyanides.
Scheme 11: Electrochemical dehydrogenative cyclization of 1,3-dicarbonyl compounds.
Scheme 12: Plausible mechanism for the dehydrogenative cyclization of 1,3-dicarbonyl compounds.
Scheme 13: Photocatalyzed cyclization of N-arylacrylamide and N,N-dimethylaniline.
Scheme 14: Proposed mechanism for the photocatalyzed cyclization of N-arylacrylamides and N,N-dimethylanilines....
Scheme 15: Electrochemical monofluoroalkylation cyclization of N-arylacrylamides with dimethyl 2-fluoromalonat...
Scheme 16: Proposed mechanism for the electrochemical radical cyclization of N-arylacrylamides with dimethyl 2...
Scheme 17: Photoelectrocatalytic carbocyclization of unactivated alkenes using simple malonates.
Scheme 18: Plausible mechanism for the photoelectrocatalytic carbocyclization of unactivated alkenes with simp...
Scheme 19: Bromide-catalyzed electrochemical trifluoromethylation/cyclization of N-arylacrylamides.
Scheme 20: Proposed mechanism for the electrochemical trifluoromethylation/cyclization of N-arylacrylamides.
Scheme 21: Visible light-mediated trifluoromethylarylation of N-arylacrylamides.
Scheme 22: Plausible reaction mechanism for the visible light-mediated trifluoromethylarylation of N-arylacryl...
Scheme 23: Electrochemical difluoroethylation cyclization of N-arylacrylamides with sodium difluoroethylsulfin...
Scheme 24: Electrochemical difluoroethylation cyclization of N-methyacryloyl-N-alkylbenzamides with sodium dif...
Scheme 25: Photoredox-catalyzed radical aryldifluoromethylation of N-arylacrylamides with S-(difluoromethyl)su...
Scheme 26: Proposed mechanism for the photoredox-catalyzed radical aryldifluoromethylation of N-arylacrylamide...
Scheme 27: Visible-light-induced domino difluoroalkylation/cyclization of N-cyanamide alkenes.
Scheme 28: Proposed mechanism of photoredox-catalyzed radical domino difluoroalkylation/cyclization of N-cyana...
Scheme 29: Palladium-catalyzed oxidative difunctionalization of alkenes.
Scheme 30: Two possible mechanisms of palladium-catalyzed oxidative difunctionalization.
Scheme 31: Silver-catalyzed oxidative 1,2-alkyletherification of unactivated alkenes with α-bromoalkylcarbonyl...
Scheme 32: Photochemical radical cascade cyclization of dienes.
Scheme 33: Proposed mechanism for the photochemical radical cascade 6-endo cyclization of dienes with α-carbon...
Scheme 34: Photocatalyzed radical coupling/cyclization of N-arylacrylamides and.
Scheme 35: Photocatalyzed radical-type couplings/cyclization of N-arylacrylamides with sulfoxonium ylides.
Scheme 36: Possible mechanism of visible-light-induced radical-type couplings/cyclization of N-arylacrylamides...
Scheme 37: Visible-light-promoted difluoroalkylated oxindoles systhesis via EDA complexes.
Scheme 38: Possible mechanism for the visible-light-promoted radical cyclization of N-arylacrylamides with bro...
Scheme 39: A dicumyl peroxide-initiated radical cascade reaction of N-arylacrylamide with DCM.
Scheme 40: Possible mechanism of radical cyclization of N-arylacrylamides with DCM.
Scheme 41: An AIBN-mediated radical cascade reaction of N-arylacrylamides with perfluoroalkyl iodides.
Scheme 42: Possible mechanism for the reaction with perfluoroalkyl iodides.
Scheme 43: Photoinduced palladium-catalyzed radical annulation of N-arylacrylamides with alkyl halides.
Scheme 44: Radical alkylation/cyclization of N-Alkyl-N-methacryloylbenzamides with alkyl halides.
Scheme 45: Possible mechanism for the alkylation/cyclization with unactivated alkyl chlorides.
Scheme 46: Visible-light-driven palladium-catalyzed radical cascade cyclization of N-arylacrylamides with unac...
Scheme 47: NHC-catalyzed radical cascade cyclization of N-arylacrylamides with alkyl bromides.
Scheme 48: Possible mechanism of NHC-catalyzed radical cascade cyclization.
Scheme 49: Electrochemically mediated radical cyclization reaction of N-arylacrylamides with freon-type methan...
Scheme 50: Proposed mechanistic pathway of electrochemically induced radical cyclization reaction.
Scheme 51: Redox-neutral photoinduced radical cascade cylization of N-arylacrylamides with unactivated alkyl c...
Scheme 52: Proposed mechanistic hypothesis of redox-neutral radical cascade cyclization.
Scheme 53: Thiol-mediated photochemical radical cascade cylization of N-arylacrylamides with aryl halides.
Scheme 54: Proposed possible mechanism of thiol-mediated photochemical radical cascade cyclization.
Scheme 55: Visible-light-induced radical cascade bromocyclization of N-arylacrylamides with NBS.
Scheme 56: Possible mechanism of visible-light-induced radical cascade cyclization.
Scheme 57: Decarboxylation/radical C–H functionalization by visible-light photoredox catalysis.
Scheme 58: Plausible mechanism of visible-light photoredox-catalyzed radical cascade cyclization.
Scheme 59: Visible-light-promoted tandem radical cyclization of N-arylacrylamides with N-(acyloxy)phthalimides....
Scheme 60: Plausible mechanism for the tandem radical cyclization reaction.
Scheme 61: Visible-light-induced aerobic radical cascade alkylation/cyclization of N-arylacrylamides with alde...
Scheme 62: Plausible mechanism for the aerobic radical alkylarylation of electron-deficient amides.
Scheme 63: Oxidative decarbonylative [3 + 2]/[5 + 2] annulation of N-arylacrylamide with vinyl acids.
Scheme 64: Plausible mechanism for the decarboxylative (3 + 2)/(5 + 2) annulation between N-arylacrylamides an...
Scheme 65: Rhenium-catalyzed alkylarylation of alkenes with PhI(O2CR)2.
Scheme 66: Plausible mechanism for the rhenium-catalyzed decarboxylative annulation of N-arylacrylamides with ...
Scheme 67: Visible-light-induced one-pot tandem reaction of N-arylacrylamides.
Scheme 68: Plausible mechanism for the visible-light-initiated tandem synthesis of difluoromethylated oxindole...
Scheme 69: Copper-catalyzed redox-neutral cyanoalkylarylation of activated alkenes with cyclobutanone oxime es...
Scheme 70: Plausible mechanism for the copper-catalyzed cyanoalkylarylation of activated alkenes.
Scheme 71: Photoinduced alkyl/aryl radical cascade for the synthesis of quaternary CF3-attached oxindoles.
Scheme 72: Plausible photoinduced electron-transfer (PET) mechanism.
Scheme 73: Photoinduced cerium-mediated decarboxylative alkylation cascade cyclization.
Scheme 74: Plausible reaction mechanism for the decarboxylative radical-cascade alkylation/cyclization.
Scheme 75: Metal-free oxidative tandem coupling of activated alkenes.
Scheme 76: Control experiments and possible mechanism for 1,2-carbonylarylation of alkenes with carbonyl C(sp2...
Scheme 77: Silver-catalyzed acyl-arylation of activated alkenes with α-oxocarboxylic acids.
Scheme 78: Proposed mechanism for the decarboxylative acylarylation of acrylamides.
Scheme 79: Visible-light-mediated tandem acylarylation of olefines with carboxylic acids.
Scheme 80: Proposed mechanism for the radical cascade cyclization with acyl radical via visible-light photored...
Scheme 81: Erythrosine B-catalyzed visible-light photoredox arylation-cyclization of N-arylacrylamides with ar...
Scheme 82: Electrochemical cobalt-catalyzed radical cyclization of N-arylacrylamides with arylhydrazines or po...
Scheme 83: Proposed mechanism of radical cascade cyclization via electrochemical cobalt catalysis.
Scheme 84: Copper-catalyzed oxidative tandem carbamoylation/cyclization of N-arylacrylamides with hydrazinecar...
Scheme 85: Proposed reaction mechanism for the radical cascade cyclization by copper catalysis.
Scheme 86: Visible-light-driven radical cascade cyclization reaction of N-arylacrylamides with α-keto acids.
Scheme 87: Proposed mechanism of visible-light-driven cascade cyclization reaction.
Scheme 88: Peroxide-induced radical carbonylation of N-(2-methylallyl)benzamides with methyl formate.
Scheme 89: Proposed cyclization mechanism of peroxide-induced radical carbonylation with N-(2-methylallyl)benz...
Scheme 90: Persulfate promoted carbamoylation of N-arylacrylamides and N-arylcinnamamides.
Scheme 91: Proposed mechanism for the persulfate promoted radical cascade cyclization reaction of N-arylacryla...
Scheme 92: Photocatalyzed carboacylation with N-arylpropiolamides/N-alkyl acrylamides.
Scheme 93: Plausible mechanism for the photoinduced carboacylation of N-arylpropiolamides/N-alkyl acrylamides.
Scheme 94: Electrochemical Fe-catalyzed radical cyclization with N-arylacrylamides.
Scheme 95: Plausible mechanism for the electrochemical Fe-catalysed radical cyclization of N-phenylacrylamide.
Scheme 96: Substrate scope of the selective functionalization of various α-ketoalkylsilyl peroxides with metha...
Scheme 97: Proposed reaction mechanism for the Fe-catalyzed reaction of alkylsilyl peroxides with methacrylami...
Scheme 98: EDA-complex mediated C(sp2)–C(sp3) cross-coupling of TTs and N-methyl-N-phenylmethacrylamides.
Scheme 99: Proposed mechanism for the synthesis of oxindoles via EDA complex.
Supramolecular assembly of hypervalent iodine macrocycles and alkali metals
- Krishna Pandey,
- Lucas X. Orton,
- Grayson Venus,
- Waseem A. Hussain,
- Toby Woods,
- Lichang Wang and
- Kyle N. Plunkett
Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87
- bonding is characterized as those interactions that involve intermolecular hypervalent connections with lengths shorter than the sum of the van der Waals radii between a heavy p-block element and an electron-pair donor (typically O, N, S, or halogen) [15]. Secondary I···O interactions have been found to
Graphical Abstract
Figure 1: (A) Our previous work: Assembly and disassembly of phenylalanine hypervalent iodine macrocycles (Ph...
Figure 2: Two conformations of the HIM were found. One conformation projected all three benzyl groups in a ve...
Figure 3: A) Chemical structure of HIM 1: Three iodine atoms and three inward projected ester carbonyls curcu...
Figure 4: 1H NMR titration experiment of 1 with LiBArF20 at an incremental equivalency in CDCl3 and (CD3)2CO ...
Figure 5: Crystal structures of HIM 1 and LiBArF20 (A) and NaBArF24 (B). BARF cation is omitted for clarity. ...
Figure 6: Alternative view of the crystal structure of the HIM 1 and LiBArF20 complex. BArF20 anion is omitte...
Figure 7: Isotherms of 1 titrated with NaBArF24 orLiBArF20. The solid lines are the predicted model fits for ...
Figure 8: Lithium complex 2 (red) overlaid with lithium complex 3 (blue). In lithium complex 2, one benzyl ri...
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
- styrenes with alkyl formates and the oxidant 4-cyano-1-(1-methylethoxy)pyridinium trifluoromethanesulfonate to give the corresponding cinnamate esters 185–192 via intermolecular addition of styrene to an alkoxyradical forming radical adduct 193 (Scheme 59) [102]. Iwasawa and co-workers (2020) employed CO2
- )-cinnamic acid esters 445–448 in excellent yields via E-to-Z photoisomerization mediated by the photocatalyst (Scheme 90) [152]. Nguyen and co-workers (2019) employed iodine to catalyze the intermolecular olefin-carbonyl metathesis reaction of benzaldehyde (449) and acrylate 450 to give the corresponding
Graphical Abstract
Figure 1: Biologically active cinnamic acid derivatives.
Scheme 1: General synthetic strategies for cinnamic acid derivatizations.
Scheme 2: Cinnamic acid coupling via isobutyl anhydride formation.
Scheme 3: Amidation reaction via O/N-pivaloyl activation.
Scheme 4: Cinnamic acid amidation using TCCA/PPh3 reagent.
Scheme 5: Cinnamic acid amidation using triazine-based reagents.
Scheme 6: Cinnamic acid amidation using continuous flow mechanochemistry.
Scheme 7: Cinnamic acid amidation using COMU as coupling reagent.
Scheme 8: Cinnamic acid amidation using allenone coupling reagent.
Scheme 9: Cinnamic acid amidation using 4-acetamidophenyl triflimide as reagent.
Scheme 10: Cinnamic acid amidation using methyltrimethoxysilane (MTM).
Scheme 11: Cinnamic acid amidation utilizing amine–borane reagent.
Scheme 12: Cinnamic acid amidation using TCCA/PPh3 reagent.
Scheme 13: Cinnamic acid amidation using PPh3/I2 reagent.
Scheme 14: Cinnamic acid amidation using PCl3 reagent.
Scheme 15: Cinnamic acid amidation utilizing pentafluoropyridine (PFP) as reagent.
Scheme 16: Cinnamic acid amidation using hypervalent iodine(III).
Scheme 17: Mechanochemical amidation using 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) reagent.
Scheme 18: Methyl ester preparation using tris(2,4,6-trimethoxyphenyl)phosphine (TMPP).
Scheme 19: N-Trifluoromethyl amide preparation using isothiocyanate and AgF.
Scheme 20: POCl3-mediated amide coupling of carboxylic acid and DMF.
Scheme 21: O-Alkylation of cinnamic acid using alkylating agents.
Scheme 22: Glycoside preparation via Mitsunobu reaction.
Scheme 23: O/N-Acylation via rearrangement reactions.
Scheme 24: Amidation reactions using sulfur-based alkylating agents.
Scheme 25: Amidation reaction catalyzed by Pd0 via C–N cleavage.
Scheme 26: Amidation reaction catalyzed by CuCl/PPh3.
Scheme 27: Cu(II) triflate-catalyzed N-difluoroethylimide synthesis.
Scheme 28: Cu/Selectfluor-catalyzed transamidation reaction.
Scheme 29: CuO–CaCO3-catalyzed amidation reaction.
Scheme 30: Ni-catalyzed reductive amidation.
Scheme 31: Lewis acidic transition-metal-catalyzed O/N-acylations.
Scheme 32: Visible-light-promoted amidation of cinnamic acid.
Scheme 33: Sunlight/LED-promoted amidation of cinnamic acid.
Scheme 34: Organophotocatalyst-promoted N–O cleavage of Weinreb amides to synthesize primary amides.
Scheme 35: Cinnamamide synthesis through [Ir] photocatalyst-promoted C–N-bond cleavage of tertiary amines.
Scheme 36: Blue LED-promoted FeCl3-catalyzed reductive transamidation.
Scheme 37: FPyr/TCT-catalyzed amidation of cinnamic acid derivative 121.
Scheme 38: Cs2CO3/DMAP-mediated esterification.
Scheme 39: HBTM organocatalyzed atroposelective N-acylation.
Scheme 40: BH3-catalyzed N-acylation reactions.
Scheme 41: Borane-catalyzed N-acylation reactions.
Scheme 42: Catalytic N-acylation reactions via H/F bonding activation.
Scheme 43: Brønsted base-catalyzed synthesis of cinnamic acid esters.
Scheme 44: DABCO/Fe3O4-catalyzed N-methyl amidation of cinnamic acid 122.
Scheme 45: Catalytic oxidation reactions of acylating agents.
Scheme 46: Preparation of cinnamamide-substituted benzocyclooctene using I(I)/I(III) catalysis.
Scheme 47: Pd-colloids-catalyzed oxidative esterification of cinnamyl alcohol.
Scheme 48: Graphene-supported Pd/Au alloy-catalyzed oxidative esterification via hemiacetal intermediate.
Scheme 49: Au-supported on A) carbon nanotubes (CNT) and B) on porous boron nitride (pBN) as catalyst for the ...
Scheme 50: Cr-based catalyzed oxidative esterification of cinnamyl alcohols with H2O2 as the oxidant.
Scheme 51: Co-based catalysts used for oxidative esterification of cinnamyl alcohol.
Scheme 52: Iron (A) and copper (B)-catalyzed oxidative esterification of cinnamaldehyde.
Scheme 53: NiHPMA-catalyzed oxidative esterification of cinnamaldehyde.
Scheme 54: Synthesis of cinammic acid esters through NHC-catalyzed oxidative esterification via intermolecular...
Scheme 55: Redox-active NHC-catalyzed esterification via intramolecular oxidation.
Scheme 56: Electrochemical conversion of cinnamaldehyde to methyl cinnamate.
Scheme 57: Bu4NI/TBHP-catalyzed synthesis of bisamides from cinnamalaldehyde N-tosylhydrazone.
Scheme 58: Zn/NC-950-catalyzed oxidative esterification of ketone 182.
Scheme 59: Ru-catalyzed oxidative carboxylation of terminal alkenes.
Scheme 60: Direct carboxylation of alkenes using CO2.
Scheme 61: Carboxylation of alkenylboronic acid/ester.
Scheme 62: Carboxylation of gem-difluoroalkenes with CO2.
Scheme 63: Photoredox-catalyzed carboxylation of difluoroalkenes.
Scheme 64: Ru-catalyzed carboxylation of alkenyl halide.
Scheme 65: Carboxylation of alkenyl halides under flow conditions.
Scheme 66: Cinnamic acid ester syntheses through carboxylation of alkenyl sulfides/sulfones.
Scheme 67: Cinnamic acid derivatives synthesis through a Ag-catalyzed decarboxylative cross-coupling proceedin...
Scheme 68: Pd-catalyzed alkyne hydrocarbonylation.
Scheme 69: Fe-catalyzed alkyne hydrocarbonylation.
Scheme 70: Alkyne hydrocarboxylation using CO2.
Scheme 71: Alkyne hydrocarboxylation using HCO2H as CO surrogate.
Scheme 72: Co/AlMe3-catalyzed alkyne hydrocarboxylation using DMF.
Scheme 73: Au-catalyzed oxidation of Au–allenylidenes.
Scheme 74: Pd-catalyzed C–C-bond activation of cyclopropenones to synthesize unsaturated esters and amides.
Scheme 75: Ag-catalyzed C–C-bond activation of diphenylcyclopropenone.
Scheme 76: Cu-catalyzed C–C bond activation of diphenylcyclopropenone.
Scheme 77: PPh3-catalyzed C–C-bond activation of diphenylcyclopropenone.
Scheme 78: Catalyst-free C–C-bond activation of diphenylcyclopropenone.
Scheme 79: Cu-catalyzed dioxolane cleavage.
Scheme 80: Multicomponent coupling reactions.
Scheme 81: Pd-catalyzed partial hydrogenation of electrophilic alkynes.
Scheme 82: Nickel and cobalt as earth-abundant transition metals used as catalysts for the partial hydrogenati...
Scheme 83: Metal-free-catalyzed partial hydrogenation of conjugated alkynes.
Scheme 84: Horner–Wadsworth–Emmons reaction between triethyl 2-fluoro-2-phosphonoacetate and aldehydes with ei...
Scheme 85: Preparation of E/Z-cinnamates using thiouronium ylides.
Scheme 86: Transition-metal-catalyzed ylide reactions.
Scheme 87: Redox-driven ylide reactions.
Scheme 88: Noble transition-metal-catalyzed olefination via carbenoid species.
Scheme 89: TrBF4-catalyzed olefination via carbene species.
Scheme 90: Grubbs catalyst (cat 7)/photocatalyst-mediated metathesis reactions.
Scheme 91: Elemental I2-catalyzed carbonyl-olefin metathesis.
Scheme 92: Cu-photocatalyzed E-to-Z isomerization of cinnamic acid derivatives.
Scheme 93: Ni-catalyzed E-to-Z isomerization.
Scheme 94: Dehydration of β-hydroxy esters via an E1cB mechanism to access (E)-cinnamic acid esters.
Scheme 95: Domino ring-opening reaction induced by a base.
Scheme 96: Dehydroamination of α-aminoester derivatives.
Scheme 97: Accessing methyl cinnamate (44) via metal-free deamination or decarboxylation.
Scheme 98: The core–shell magnetic nanosupport-catalyzed condensation reaction.
Scheme 99: Accessing cinnamic acid derivatives from acetic acid esters/amides through α-olefination.
Scheme 100: Accessing cinnamic acid derivatives via acceptorless α,β-dehydrogenation.
Scheme 101: Cu-catalyzed formal [3 + 2] cycloaddition.
Scheme 102: Pd-catalyzed C–C bond formation via 1,4-Pd-shift.
Scheme 103: NHC-catalyzed Rauhut–Currier reactions.
Scheme 104: Heck-type reaction for Cα arylation.
Scheme 105: Cu-catalyzed trifluoromethylation of cinnamamide.
Scheme 106: Ru-catalyzed alkenylation of arenes using directing groups.
Scheme 107: Earth-abundant transition-metal-catalyzed hydroarylation of α,β-alkynyl ester 374.
Scheme 108: Precious transition-metal-catalyzed β-arylation of cinnamic acid amide/ester.
Scheme 109: Pd-catalyzed β-amination of cinnamamide.
Scheme 110: S8-mediated β-amination of methyl cinnamate (44).
Scheme 111: Pd-catalyzed cross-coupling reaction of alkynyl esters with phenylsilanes.
Scheme 112: Pd-catalyzed β-cyanation of alkynyl amide/ester.
Scheme 113: Au-catalyzed β-amination of alkynyl ester 374.
Scheme 114: Metal-free-catalyzed Cβ-functionalizations of alkynyl esters.
Scheme 115: Heck-type reactions.
Scheme 116: Mizoroki–Heck coupling reactions using unconventional functionalized arenes.
Scheme 117: Functional group-directed Mizoroki–Heck coupling reactions.
Scheme 118: Pd nanoparticles-catalyzed Mizoroki–Heck coupling reactions.
Scheme 119: Catellani-type reactions to access methyl cinnamate with multifunctionalized arene.
Scheme 120: Multicomponent coupling reactions.
Scheme 121: Single atom Pt-catalyzed Heck coupling reaction.
Scheme 122: Earth-abundant transition metal-catalyzed Heck coupling reactions.
Scheme 123: Polymer-coated earth-abundant transition metals-catalyzed Heck coupling reactions.
Scheme 124: Earth-abundant transition-metal-based nanoparticles as catalysts for Heck coupling reactions.
Scheme 125: CN- and Si-based directing groups to access o-selective cinnamic acid derivatives.
Scheme 126: Amide-based directing group to access o-selective cinnamic acid derivatives.
Scheme 127: Carbonyl-based directing group to access o-selective cinnamic acid derivatives.
Scheme 128: Stereoselective preparation of atropisomers via o-selective C(sp2)–H functionalization.
Scheme 129: meta-Selective C(sp2)–H functionalization using directing group-tethered arenes.
Scheme 130: para-Selective C(sp2)–H functionalization using directing group-tethered arenes.
Scheme 131: Non-directed C(sp2)–H functionalization via electrooxidative Fujiwara–Moritani reaction.
Scheme 132: Interconversion of functional groups attached to cinnamic acid.
Scheme 133: meta-Selective C(sp2)–H functionalization of cinnamate ester.
Scheme 134: C(sp2)–F arylation using Grignard reagents.
Scheme 135: Truce–Smiles rearrangement of N-aryl metacrylamides.
Scheme 136: Phosphine-catalyzed cyclization of γ-vinyl allenoate with enamino esters.
Recent advances in controllable/divergent synthesis
- Jilei Cao,
- Leiyang Bai and
- Xuefeng Jiang
Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73
- achieved selective synthesis of either enantiomer of a target product by controlling the reaction duration (Scheme 13) [42]. When performing the asymmetric intermolecular allylic amination of 6-hydroxyisoquinoline (49) with tert-butyl(1-phenylallyl)carbonate ((rac)-50) using an Ir catalyst derived from [Ir
Graphical Abstract
Scheme 1: Ligand-controlled regiodivergent C1 insertion into arynes [19].
Scheme 2: Ligand effect in homogenous gold catalysis enabling regiodivergent π-bond-activated cyclization [20].
Scheme 3: Ligand-controlled palladium(II)-catalyzed regiodivergent carbonylation of alkynes [21].
Scheme 4: Catalyst-controlled annulations of strained cyclic allenes with π-allyl palladium complexes and pro...
Scheme 5: Ring expansion of benzosilacyclobutenes with alkynes [23].
Scheme 6: Photoinduced regiodivergent and enantioselective cross-coupling [24].
Scheme 7: Catalyst-controlled regiodivergent and enantioselective formal hydroamination of N,N-disubstituted ...
Scheme 8: Catalyst-tuned regio- and enantioselective C(sp3)–C(sp3) coupling [31].
Scheme 9: Catalyst-controlled annulations of bicyclo[1.1.0]butanes with vinyl azides [32].
Scheme 10: Solvent-driven reversible macrocycle-to-macrocycle interconversion [39].
Scheme 11: Unexpected solvent-dependent reactivity of cyclic diazo imides and mechanism [40].
Scheme 12: Palladium-catalyzed annulation of prochiral N-arylphosphonamides with aromatic iodides [41].
Scheme 13: Time-dependent enantiodivergent synthesis [42].
Scheme 14: Time-controlled palladium-catalyzed divergent synthesis of silacycles via C–H activation [43].
Scheme 15: Proposed mechanism for the time-controlled palladium-catalyzed divergent synthesis of silacycles [43].
Scheme 16: Metal-free temperature-controlled regiodivergent borylative cyclizations of enynes [45].
Scheme 17: Nickel-catalyzed switchable site-selective alkene hydroalkylation by temperature regulation [46].
Scheme 18: Copper-catalyzed decarboxylative amination/hydroamination sequence [48].
Scheme 19: Proposed mechanism of copper-catalyzed decarboxylative amination/hydroamination sequence [48].
Scheme 20: Enantioselective chemodivergent three-component radical tandem reactions [49].
Scheme 21: Substrate-controlled synthesis of indoles and 3H-indoles [52].
Scheme 22: Controlled mono- and double methylene insertions into nitrogen–boron bonds [53].
Scheme 23: Copper-catalyzed substrate-controlled carbonylative synthesis of α-keto amides and amides [54].
Scheme 24: Divergent sulfur(VI) fluoride exchange linkage of sulfonimidoyl fluorides and alkynes [55].
Scheme 25: Modular and divergent syntheses of protoberberine and protonitidine alkaloids [56].
Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions
- Wen-Hui Mi,
- Teng-Yu Huang,
- Xu-Dong Wang,
- Yu-Fei Ao,
- Qi-Qiang Wang and
- De-Xian Wang
Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72
- , while the glycol chains are oriented along the long axis in the opposite orientations. In packing mode, the submacrocycle units form close contacts through intermolecular hydrogen bonding, C–H···π, and lone pair–π interactions, resulting in a 1D linear assembly. Anion recognition With the functional
Graphical Abstract
Scheme 1: Synthesis of ultracycles.
Figure 1: (a, b) Crystal structure of B4aH (hydrogen atoms are omitted for clarity), and (c) the stacking str...
Figure 2: (a) The structures of host and guests, (b) 1H NMR spectra (298 K, 400 MHz, CD3CN) of B4aH upon titr...
Figure 3: (a–c) DFT-optimized structure of the B4aH-C72− complex. The blue dotted lines represent hydrogen bo...
Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters
- Lewis McGhie,
- Hannah M. Kortman,
- Jenna Rumpf,
- Peter H. Seeberger and
- John J. Molloy
Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69
- process (Figure 2B) [19]. In a bid to translate sensitization reaction probes to meaningful synthetic transformations, conventional intermolecular [2 + 2] cycloaddition reactions were initially trialled (Figure 3A). Preliminary reactions using styrene or methyl acrylate were unsuccessful, with no [2 + 2
- ] cycloaddition observed, despite the use of higher catalyst loadings. The efficient isomerization of 1a during these reactions indicated that substrate lifetime for efficient intermolecular reactivity may be problematic. While substrate-tethered reactivity, developed by Brown and co-workers was unsuccessful [49
- as an operational mechanism. While intermolecular alkene quenching to enable [2 + 2] cycloaddition was inefficient, presumably due to poor substrate lifetime, intramolecular [2 + 2] reactivity with both acrylates and alkenylboronic esters was effective. The small 3D, boron-containing fragments could
Graphical Abstract
Figure 1: A) Energy transfer catalysis of alkenes in organic synthesis. B) Energy transfer catalysis of conju...
Figure 2: Probing boron effects on reactivity (A) and confirming the generation of a photostationary state eq...
Figure 3: Probing EnT catalysis enabled [2 + 2] cycloaddition of simple alkenylboronic esters.
Scheme 1: Establishing the substrate scope. Conditions: 3 (1 equiv), xanthone (20 mol %), MeCN (0.03 M), unde...
Scheme 2: A) Product derivatization and B) transition-metal EnT catalysis. Reaction conditions A): 4d (1 equi...
Unraveling cooperative interactions between complexed ions in dual-host strategy for cesium salt separation
- Zhihua Liu,
- Ya-Zhi Chen,
- Ji Wang,
- Qingling Nie,
- Wei Zhao and
- Biao Wu
Beilstein J. Org. Chem. 2025, 21, 845–853, doi:10.3762/bjoc.21.68
- six Cs–O ion-dipole interactions (2.9 Å and 3.2 Å). These intermolecular interactions of Cs+ cations with18-crown-6 and hexaurea receptors help to form 3D framework in the solid state (Supporting Information File 1, Figure S2), which may reinforce cooperative interactions between complexed Cs+ and
- with 18-crown-6 and tripodal receptor (CCDC: 2411575) and (b) chemical structures for three types of intermolecular interactions with complexed Cs+. (c) IGM plot illustrating the attraction between complexed Cs+ and complexed phosphate. Color coding in the range of −0.5 < ρ sign(λ2) < 0.5 a.u. Atom
Graphical Abstract
Figure 1: (a) Schematic illustration of the dual-host strategy for ion pair extraction via solid–liquid metho...
Figure 2: Single crystal structure of complexed Cs2SO4 with 18-crown-6 and tripodal receptor L (CCDC: 2411573...
Figure 3: Stacked 1H NMR spectra of (a) free anion receptor L and its complexes with one equivalent of (b) Cs2...
Figure 4: Single crystal structure of complexed Cs2CO3 (CCDC: 2411574) with 18-crown-6 and tripodal receptor L...
Figure 5: (a) Single crystal structure of complexed Cs3PO4 with 18-crown-6 and tripodal receptor (CCDC: 24115...
Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones
- Carola Tortora,
- Christian A. Fischer,
- Sascha Kohlbauer,
- Alexandru Zamfir,
- Gerd M. Ballmann,
- Jürgen Pahl,
- Sjoerd Harder and
- Svetlana B. Tsogoeva
Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59
- –(Ca) five-ring. This initial product is consumed in a tautomerization step to give slightly more stable 11, in which the cyanide group is no longer bound to the calcium atom. Tautomerization 10 → 11 (with Nβ hydrogen shifting to Nα, the former imine nitrogen) is most likely intermolecular, as direct
Graphical Abstract
Figure 1: Crystal structure of the calcium diphenyl phosphate complex 4. Hydrogen atoms are omitted for clari...
Scheme 1: Synthesis of the calcium diphenyl phosphate model complex 4 from phosphoric acid 3 and Ca(OiPr)2.
Figure 2: (A) Proposed catalytic cycle for the hydrocyanation of hydrazones with the Ca–BINOL phosphate catal...
Figure 3: Reaction energy profile for the hydrocyanation of Z-hydrazone 1, (depicted is the pathway that give...
Figure 4: Transition-state structure TS 8 for internal rotation, mixing conformational (Z/E)-pathways with op...
Figure 5: Replacement step after internal rotation in 11 via TS8 and reaction with TMSCN to give adduct 13 (s...
