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Search for "complexity" in Full Text gives 380 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Isoorotamide-based peptide nucleic acid nucleobases with extended linkers aimed at distal base recognition of adenosine in double helical RNA
- Grant D. Walby,
- Brandon R. Tessier,
- Tristan L. Mabee,
- Jennah M. Hoke,
- Hallie M. Bleam,
- Angelina Giglio-Tos,
- Emily E. Harding,
- Vladislavs Baskevics,
- Martins Katkevics,
- Eriks Rozners and
- James A. MacKay
Beilstein J. Org. Chem. 2025, 21, 2513–2523, doi:10.3762/bjoc.21.193
- that add more complexity to triplex formation. Conclusion Overall, three new PNA monomers were synthesized and incorporated into PNA oligonucleotides. Db monomers demonstrated a lack of strong affinity for the U–A base pair in dhRNA. However, selectivity of Db1 and Db3 for the intended U–A base pair
- efficient binding and further underscore the complexity of these systems due to conformational and energetic preferences. Taken together with previous studies, we postulate that future nucleobases should be designed to overcome the positional challenges related to entropy and geometry. (a) Structure of a
Graphical Abstract
Figure 1: (a) Structure of a PNA oligomer with the N-(2-aminoethyl)glycine backbone (in red); (b) Representat...
Figure 2: Representative extended nucleobase triples through Hoogsteen hydrogen bonding (blue dashed lines). ...
Figure 3: Evolution of the strategy for U–A recognition.
Figure 4: Isoorotamide-derived nucleobases for A–U recognition.
Figure 5: Proposed isoorotamide distal binding (Db) nucleobases designed from the Io5 core. Hydrogen bonding ...
Scheme 1: Synthesis of the Db1 monomer (8).
Scheme 2: Synthesis of Db2 monomer 15.
Scheme 3: Synthesis of Db3 monomer 21.
Figure 6: Sequences for RNA hairpins and PNA ligands used for binding studies.
Figure 7: Major-groove view of hydrogen-bonding interactions in the (A) Db1*U–A triplet, (B) Db2*U–A triplet,...
Comparative analysis of complanadine A total syntheses
- Reem Al-Ahmad and
- Mingji Dai
Beilstein J. Org. Chem. 2025, 21, 2334–2344, doi:10.3762/bjoc.21.178
- ; Introduction Natural products, owing to their structural complexity, diversity, and therapeutic potential, have continued to serve as inspirations for the development of novel synthetic methodologies and strategies. In turn, these methodological and strategic advancements have significantly improved the
Graphical Abstract
Scheme 1: Complanadine natural products and their plausible biosynthesis.
Scheme 2: The Siegel total synthesis of complanadine A enabled by [2 + 2 + 2] cycloadditions.
Scheme 3: The Sarpong total synthesis of complanadine A enabled by a biomimetic strategy and C–H activation.
Scheme 4: The Tsukano total synthesis of complanadine A enabled by Diels–Alder cycloaddition, Heck cyclizatio...
Scheme 5: The Dai total synthesis of complanadine A using single-atom skeletal editing.
Scheme 6: Comparative summary of the four complanadine A total syntheses.
A m-quaterphenyl probe for absolute configurational assignments of primary and secondary amines
- Yuka Takeuchi,
- Mutsumi Kobayashi,
- Yuuka Gotoh,
- Mari Ikeda,
- Yoichi Habata,
- Tomohiko Shirai and
- Shunsuke Kuwahara
Beilstein J. Org. Chem. 2025, 21, 2211–2219, doi:10.3762/bjoc.21.168
- ]. However, its use in the analysis of chiral amines has been restricted, largely due to the complexity arising from their conformational flexibility [3]. Circular dichroism (CD) spectroscopy offers a highly sensitive technique for stereochemical analysis at the microgram scale [4][5][6]. In particular
- amines. In this work, we report that the method was applied to chiral amino alcohols and amino acid esters. We also applied the method to chiral secondary amines, for which it is generally difficult to determine the absolute configuration due to the conformational complexity of their derivatives [33]. By
Graphical Abstract
Scheme 1: Coupling reaction of 1 and chiral primary and secondary amines. The central biphenyl moiety rotates...
Figure 1: CD and UV spectra of (a) tertiary amines (S)-2a–e and (b) quaternary ammonium salts (S)-2f,g and (R...
Figure 2: Schematic representation of the preferred conformation of (S)-2a.
Figure 3: Four major conformers of (S)-3a based on B3LYP/6-31G* level.
Figure 4: Four major conformers of (S)-3f based on B3LYP/6-31G* level.
Figure 5: The distribution of conformers of (S)-3a–h against dihedral angles ϕ (C6–C1–C1'–C6') calculated by ...
Figure 6: Crystal structure of (S)-2b. Four conformers exist in the unit cell. Hydrogen atoms are omitted for...
Figure 7: The relationship between the ACD values and excess of P conformer. Excess of P conformer (%) = ([P]...
Bioinspired total syntheses of natural products: a personal adventure
- Zhengyi Qin,
- Yuting Yang,
- Nuran Yan,
- Xinyu Liang,
- Zhiyu Zhang,
- Yaxuan Duan,
- Huilin Li and
- Xuegong She
Beilstein J. Org. Chem. 2025, 21, 2048–2061, doi:10.3762/bjoc.21.160
- , people began to be aware of the capability of mankind in making natural organic molecules. Since then, organic scientists are brave to challenge the complex organic structure of natural products given by nature [2][3][4][5]. To achieve the growing structural complexity of natural products, the synthetic
- ] (Figure 1). The bioinspired total synthesis literally showed the great power to gain complexity. In the 21st century, biomimetic or bioinspired synthesis has been widely realized as a powerful concept approach to natural product total synthesis, and a lot of total synthetic works of this kind have been
- reported. A bioinspired approach represents many advantages to bring benefits to total synthesis. It could rapidly achieve complexity of the target molecule from a much simpler precursor in diverse forms of transformations such as cascade reaction, cycloaddition, and C–H functionalization, thereby, shorten
Graphical Abstract
Figure 1: Representative natural products with biomimetic total synthesis.
Scheme 1: Bioinspired total synthesis of chabranol (2010).
Scheme 2: Proposed biosynthetic pathway of monocerin-family natural products.
Scheme 3: Bioinspired total synthesis of monocerin-family molecules (2013).
Scheme 4: Bioinspired skeletal diversification of (12-MeO-)tabertinggine (2016).
Scheme 5: Structures and our proposed biosynthetic pathway of gymnothelignans.
Scheme 6: Bioinspired total synthesis of gymnothelignans (2014–2025).
Scheme 7: Bioinspired total synthesis of sarglamides (2025).
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
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...
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
- applications. The assembly of nonreducing 1,1′-linked disaccharides presents greater challenges than conventional chemical glycosylation due to the need for simultaneous control of stereochemistry at two anomeric centers. The structural complexity of natural biomolecules entailing 1,1′-disaccharides, which
- donor 79 was employed in the glycosylation reaction with anomeric lactol 119 (used in 2-fold excess to compensate for its 50% content of the undesirable α-anomer), the β,β-1,1'-linked disaccharide 120 was obtained, albeit in moderate yield due to the complexity of separating it from reaction components
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...
Continuous-flow-enabled intensification in nitration processes: a review of technological developments and practical applications over the past decade
- Feng Zhou,
- Chuansong Duanmu,
- Yanxing Li,
- Jin Li,
- Haiqing Xu,
- Pan Wang and
- Kai Zhu
Beilstein J. Org. Chem. 2025, 21, 1678–1699, doi:10.3762/bjoc.21.132
- nitration degree, with excess nitric acid driving reactivity at the cost of post-treatment complexity. Simultaneously, the molar ratio of H2SO4/HNO3 (usually 1.0–4.0) modulates acid strength and catalytic activity, necessitating effective balancing to optimize nitronium iongeneration efficiency while
- and presents significant mathematical complexity when dealing with intricate reaction systems. Long-term operation stability/stress testing: Ensuring long-term operational stability is a critical requirement for the practical implementation of continuous-flow nitration processes, particularly given
- kinetically controlled. In nitration reaction kinetics studies across liquid–liquid biphasic systems (types A–C), the complexity of kinetics studies increases progressively from type A to type C, while their applicability expands correspondingly. Kinetics models derived from type A systems are typically
Graphical Abstract
Figure 1: Three key dimensions of a complete nitration process.
Figure 2: A typical continuous-flow nitration reaction system.
Figure 3: Corrosion characteristics of common wetted materials used in continuous-flow nitration system. Note...
Figure 4: Analysis of the literature on continuous-flow nitration reaction over the past decade.
Scheme 1: Model reaction for the homogeneous nitration by nitric acid/mixed acid.
Figure 5: Safety assessment criteria for nitration reactions. Notes: apressure-independent; bno hazards arisi...
Figure 6: Guide for the investigation of continuous-flow nitration processes.
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
- substrates. Keywords: amidyl radicals; C–H; HAT reagents; hydrogen-atom-transfer; late-stage functionalization; Introduction C–H bonds are the predominant chemical bonds in organic compounds, and their direct conversion can rapidly and efficiently increase the complexity and functionality of organic
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 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
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.
Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups
- Julius Seumer,
- Nicolai Ree and
- Jan H. Jensen
Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94
- molecular architectures in pharmaceuticals, polymers, and agrochemicals. Despite advancements in directing group (DG) methodologies and computational approaches, predicting accurate regioselectivity in C–H activation poses significant difficulties due to the diversity and complexity of organic compounds
Graphical Abstract
Figure 1: Overview of the predictive workflow: For the shown substrate on the left, three unique activation s...
Figure 2: Example of the output from running the SMARTS pattern approach introduced by Tomberg et al. [9] with t...
Figure 3: An example where our algorithm found a more specific SMARTS pattern match than highlighted in Tombe...
Figure 4: An example highlighting the difficulties in prioritizing the SMARTS patterns. All three patterns ma...
Figure 5: Example of a combination of C–H bond and DG that is discarded because of the angle constraint on th...
Figure 6: Example of combinations of C–H bonds and DGs that are considered identical because of symmetry of t...
Figure 7: Example of combinations of C–H bonds and DGs that are considered identical because of symmetry of t...
Figure 8: Example of combinations of C–H bonds and DGs that are considered identical because of resonance str...
Figure 9: A: Distribution of correct (green) and wrong (red) predictions for molecules with two to five poten...
Figure 10: Molecules with five potential reaction sites that are predicted wrong by the QM workflow. The exper...
Figure 11: Predictions of reaction sites within a 1 kcal·mol−1 threshold for ten molecules are marked with a b...
Figure 12: Substrate with six potential unique reaction sites for C–H functionalization. The experimentally de...
A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids
- Zhiyang Zhang,
- Jialei Hu,
- Hanfeng Ding,
- Li Zhang and
- Peirong Rao
Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75
- as compelling targets for both therapeutic development and agrochemical innovation. Furthermore, limonoids are also renowned for their extraordinary structural complexity. For instance, the phragmalin-type limonoids represent a significant category of highly oxygenated rearranged limonoids, which
Graphical Abstract
Figure 1: Representative limonoid triterpenes.
Scheme 1: Structures and retrosynthetic analysis of krishnolides A (7) and C (8).
Scheme 2: Construction of α-iodoenone 13.
Scheme 3: Construction of aldehyde 14.
Scheme 4: Synthesis of the advanced intermediate 10 (in the X ray structure of 10 solvent molecule is omitted...
Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion
- Leon M. Friedrich and
- Thisbe K. Lindhorst
Beilstein J. Org. Chem. 2025, 21, 736–748, doi:10.3762/bjoc.21.57
- bivalent azobenzene glycosides 1 and 2 in the various isomeric states (EE, EZ, ZE, and ZZ) and the lectin FimH reach a complexity which obscures the effect of azo group isomerization. (iv) Calculated binding energies for the highest affinity isomers of 1 and 2, respectively, (−107.61 and −96.22 kcal mol−1
Graphical Abstract
Figure 1: Cartoon of the photoswitchable glycoconjugates investigated in this account. The previously describ...
Scheme 1: Synthesis of the homobivalent azobenzene glycocluster 6αMan3αMan 2. Reagents and conditions: a) BF3...
Scheme 2: Synthesis of the antennas 6βGlc 3 and 3αMan 4 (A), and 6αMan 5 (B). Reagents and conditions: a) DTT...
Figure 2: A: Wavelength-selective photoswitching of the α-ᴅ-mannopyranosyloxy-AB and -ABF4 antennas comprised...
Figure 3: Comparison of the inhibitory potencies of 1, 2, 4, and 5 in the different isomeric states. The depi...
Figure 4: Three-dimensional representation of the superimposed most stable ligand–protein complexes from IFD ...
Origami with small molecules: exploiting the C–F bond as a conformational tool
- Patrick Ryan,
- Ramsha Iftikhar and
- Luke Hunter
Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54
- , conformations in which the two C–F bonds are aligned gauche will be favoured in water due to their high molecular dipole moment. A final layer of complexity is afforded by the stereochemistry of the 1,2-difluoroalkane motif: the various conformational factors described above will aggregate differently depending
- that features both an ester moiety and an amino group will be discussed later, in section 5 of this review [112]. 4 Sugars We have examined several classes of molecules of gradually increasing complexity, progressing from alkanes (section 1) to ethers (section 2) and then alcohols (section 3
Graphical Abstract
Figure 1: Fundamental characteristics of the C–F bond.
Figure 2: Incorporation of fluorine at the end of an alkyl chain.
Figure 3: Incorporation of fluorine into the middle of a linear alkyl chain.
Figure 4: Incorporation of fluorine across much, or all, of a linear alkyl chain.
Figure 5: Incorporation of fluorine into cycloalkanes.
Figure 6: Conformational effects of introducing fluorine into an ether (geminal to oxygen).
Figure 7: Conformational effects of introducing fluorine into an ether (vicinal to oxygen).
Figure 8: Effects of introducing fluorine into alcohols (and their derivatives).
Figure 9: Controlling the ring pucker of sugars through fluorination.
Figure 10: Controlling bond rotations outside the sugar ring through fluorination.
Figure 11: Effects of incorporating fluorine into amines.
Figure 12: Effects of incorporating fluorine into amine derivatives, such as amides and sulfonamides.
Figure 13: Effects of incorporating fluorine into organocatalysts.
Figure 14: Effects of incorporating fluorine into carbonyl compounds, focusing on the “carbon side.”
Figure 15: Fluoroproline-containing peptides and proteins.
Figure 16: Further examples of fluorinated linear peptides (besides fluoroprolines). For clarity, sidechains a...
Figure 17: Fluorinated cyclic peptides.
Figure 18: Fluorine-derived conformational control in sulfur-containing compounds.
Photocatalyzed elaboration of antibody-based bioconjugates
- Marine Le Stum,
- Eugénie Romero and
- Gary A. Molander
Beilstein J. Org. Chem. 2025, 21, 616–629, doi:10.3762/bjoc.21.49
- stability, and/or a shorter ADC half-life [14]. Optimization of the drug/antibody ratio (DAR) and payload distribution/location thus becomes significant for ideal ADC design. Given the complexity of biological macromolecules, there are inherent limitations in terms of the types of reactions that can be used
- remains largely unexplored. This is primarily because of the structural complexity of antibodies, which exhibit a three-dimensional architecture and numerous potential modification sites, making selective control of functionalization sites challenging. Nonetheless, photocatalytic approaches offer a unique
- demonstrates the potency of photoinduced methods to access more homogeneous ADCs, hopefully reducing patient side effects. In summary, photoredox modifications of antibodies have gained attention in recent years, though the field is still in its early stages because of the complexity of antibody structures
Graphical Abstract
Figure 1: Representation of an antibody–drug conjugate. The antibody shown in this figure is from https://www...
Figure 2: a. Photoredox catalytic cycles; b. absorption spectrum of photosensitizers. Therapeutic window indi...
Figure 3: Graph representing the average number of publications focusing on photoredox chemistry applied to p...
Figure 4: Schematic procedure developed by Sato et al. on histidine photoinduced modification. The antibody s...
Figure 5: Schematic procedure of the divergent method developed by Sato et al. on histidine/tyrosine photoind...
Figure 6: Schematic procedure developed by Bräse et al. on photoinduced disulfide rebridging method.
Figure 7: Schematic procedure developed by Lang et al. on a photoinduced dual nickel photoredox-catalyzed app...
Figure 8: Schematic of the procedure developed by Chang et al. on photoinduced high affinity IgG Fc-binding s...
Figure 9: Potential advantages of photoredox chemistry for bioconjugation applied to antibodies. The antibody...
Figure 10: Representation of the photoinduced control of the DAR. The antibody shown in this figure is from ht...
Figure 11: Representation of a photoinduced control of multi-payloads ADC strategy. The antibody shown in this...
Formaldehyde surrogates in multicomponent reactions
- Cecilia I. Attorresi,
- Javier A. Ramírez and
- Bernhard Westermann
Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45
- the MCR product is possible thus increasing the versatility of these reactions in terms of structural diversity and molecular complexity. In this context, a wide variety of heterocycles and macrocycles as important biological scaffolds have been synthesized [6]. One of the most important components
Graphical Abstract
Scheme 1: Features of the ideal reaction (redrawn from P. A. Wender et al. [1]).
Scheme 2: Some of the most popular MCRs with formaldehyde as the carbonyl component.
Scheme 3: Ugi reaction under a catalyzed electro-oxidation process using TEMPO (2,2,6,6-tetramethyl-1-piperid...
Scheme 4: Examples of different products obtained by MCRs in which DMSO serves as -SCH3 source.
Scheme 5: Mechanism of the decomposition of DMSO under acidic or thermal conditions. a) In situ generation of...
Scheme 6: Povarov multicomponent reaction to quinolines.
Scheme 7: Example of the Povarov reaction with formaldehyde with a julolidine derivative as main product.
Scheme 8: Povarov multicomponent reaction to quinoline derivatives I and II using DMSO as formaldehyde surrog...
Scheme 9: Example of a Povarov three-component reaction with change of catalyst, yielding regioisomer III. In...
Scheme 10: The Povarov three-component reactions carried out under acidic catalysis to afford quinoline regios...
Scheme 11: Different MCR routes involving DMSO to synthesize complex heterocycles such as diarylpyridines and ...
Scheme 12: Pyrazole synthesis by a three-component reaction using DMSO as a source of a C-1 unit.
Scheme 13: Three-component reactions for the synthesis of aliphatic heterocycles 13 and 14 using DMSO as a for...
Scheme 14: Proposed mechanism for the 3CR between homoallylic amines, disulfides, and DMSO.
Scheme 15: Mannich-type reaction using DMSO as formaldehyde surrogate.
Scheme 16: Mechanism for the 3CR-Mannich-type reaction between aryl ketone 18, saccharine (19), and DMSO. The ...
Scheme 17: Mannich-type reaction using DMSO as formaldehyde surrogate and under oxidative activation.
Scheme 18: Three-component reaction between an indazole, a carboxylic acid, and DMSO.
Scheme 19: Amine–aldehyde–alkyne (AAA) coupling reaction and plausible mechanism.
Scheme 20: AHA coupling for the synthesis of propargylamines using dihalomethanes as C1 building blocks.
Scheme 21: AHA coupling using CH2Cl2 as both solvent and methylene source.
Scheme 22: Examples of propargylamines synthesized under catalytic AHA protocols.
Scheme 23: Proposed mechanism for the synthesis of propargylamines using dichloromethane as a C1 source.
Scheme 24: Mechanism proposed for the generation of the aminal intermediate E by Buckley et al. [68].
Scheme 25: Pudovic and Kabachnik–Fields reactions for the synthesis of α-aminophosphonates.
Scheme 26: a) Abramov side reaction that generates α-hydroxy phosphonate as a byproduct during the Kabachnik-F...
Scheme 27: Catalyst-free three component reaction to afford α-amino phosphorus product 35 using 1,1-dihaloalka...
Scheme 28: a) Proposed mechanism for the three-component reaction of dichloromethane, amine and phosphorus com...
Scheme 29: Ugi-ammonia strategy using HMTA as a formaldehyde surrogate.
Scheme 30: Glyoxylate and its derivatives as C1 building blocks.
Scheme 31: The Groebke–Blackburn–Bienaymé multicomponent reaction (GBB) and its mechanism.
Scheme 32: a) Byproducts in the GBB multicomponent reaction (GBB) when formaldehyde is used as the carbonyl co...
Scheme 33: Possible regioisomers in the GBB multicomponent reaction when formaldehyde is used as the carbonyl ...
Scheme 34: The multicomponent GBB reaction yields 2-unsubstituted 3-aminoimidazo heterocycles 42a using MP-gly...
Scheme 35: GBB multicomponent reaction to 2-unsubstituted 3-amino imidazo heterocycles 42a using glyoxylic aci...
Scheme 36: GBB reaction using glyoxylic acid immobilized on silica as formaldehyde surrogate.
Scheme 37: Bioactive products synthesized by the GBB reaction using glyoxylic acid.
Scheme 38: van Leusen three-component reaction to imidazoles.
Scheme 39: Side reaction during the synthesis of imidazoles with formaldehyde as the carbonyl compound.
Scheme 40: Optimization of the van Leusen three component reaction to 1,4-disubstituted imidazoles 43 using gl...
Scheme 41: Application of the Sisko strategy [96] for the synthesis of CB1 receptor antagonist compounds [97].
Scheme 42: Side reaction, when NH4OH is used as amine component.
Scheme 43: Ugi-type adducts with the ester moiety and the acidic CH to be used for post-cyclization sequences.
Scheme 44: Ugi/cycloisomerization process to pyrrolones 51, butenolides 52, and pyrroline 53.
Scheme 45: Radical cyclization reactions from Ugi adducts promoted by TEMPO.
Scheme 46: Hydrolysis and decarboxylation reactions to products with incorporation of a C1 unit of ethyl glyox...
Scheme 47: One-step synthetic route to pyrrolones 60 using phenylglyoxal.
Scheme 48: Ugi-pseudo-Knoevenagel-pseudo-Dieckmann cascade sequence for the synthesis of fused heterocycles.
Scheme 49: Ugi-pseudo-Knoevenagel reaction from ethyl glyoxylate.
Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages
- Keith G. Andrews
Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30
- quickly identified the triptycenyl-based imine cages of Mastalerz [301] as a strong starting point because: (i) they offered efficient, modular assembly; (ii) all of the complexity could be confined to the privileged triptycene motifs, which would present rigid internal vectors into the cavity for
Graphical Abstract
Figure 1: Catalytic rate enhancements from a reduction in the Gibbs free energy transition barrier can be fra...
Figure 2: Typical catalysis modes using macrocycle cavities performing (non-specific) hydrophobic substrate b...
Figure 3: (A) Cram’s serine protease model system [87,88]. The macrocycle showed strong substrate binding (organizat...
Figure 4: (A) Self-assembling capsules can perform hydrophobic catalysis [116,117]. (B) Resorcin[4]arene building bloc...
Figure 5: (A) Metal-organic cages and key modes in catalysis. (B) Charged metals or ligands can result in +/−...
Figure 6: (A) Frameworks (MOFs, COFs) can be catalysts. (B) Example of a 2D-COF, assembled by dynamic covalen...
Figure 7: (A) Examples of dynamic covalent chemistry used to synthesize organic cages. (B) Organic cages are ...
Figure 8: (A) Design and development of soluble, functionalized, robust organic cages. (B) Examples of modula...
Figure 9: (A) There are 13 metastable conformers (symmetry-corrected) for cage 1 due to permutations of amide...
The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation
- Rituparna Das and
- Balaram Mukhopadhyay
Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27
- enzymatic protocols and thus, glycoscientists mostly rely on chemical glycosylation to achieve complex oligosaccharide targets. However, chemical glycosylation remains to be a highly complex, ubiquitous and non-templated process for the synthetic chemists [19]. The inherent structural complexity of the
- glycoside 8 (Scheme 1). Glycosylation is considered as the most crucial step in any oligosaccharide synthesis, although it may be argued that, building block preparations or final deprotection steps remain equally demanding. The main challenge of glycosylation lies in the structural complexity of the
- [48]. The review will primarily be referring to axial or α-glycosides as 1,2-cis glycosides except for mannosides where the term β-mannosides will be used for 1,2-cis-mannoside configuration, respecting the complexity and novelty they bring to the world of synthetic glycochemistry. The spanning of the
Graphical Abstract
Scheme 1: Continuum in the mechanistic pathway of glycosylation [32] reactions ranging between SN2 and SN1.
Scheme 2: Formation of 1,2-trans glycosides by neighbouring group participation with acyl protection in C-2 p...
Scheme 3: Solvent-free activation [92] of disarmed per-acetylated (15) and per-benzoylated (18) glycosyl donors.
Scheme 4: Synthesis of donor 2-(2,2,2-trichloroethoxy)glucopyrano-[2,1-d]-2-oxazoline 22 [94] and regioselective ...
Scheme 5: The use of levulinoyl protection for an orthogonal glycosylation reaction.
Figure 1: The derivatives 32–36 of the pivaloyl group.
Scheme 6: Benzyl and cyanopivalolyl ester-protected hexarhamnoside derivative 37 and its global deprotection ...
Scheme 7: Orthogonal chloroacetyl group deprotection in oligosaccharide synthesis [113].
Figure 2: The derivatives of the chloroacetyl group: CAMB protection (41) [123], CAEB protection (42) [124], POMB prote...
Scheme 8: Use of the (2-nitrophenyl)acetyl protecting group [126] as the neighbouring group protecting group at th...
Scheme 9: Neighbouring group participation protocol by the BnPAc protecting group [128] in the C-2 position.
Scheme 10: Glycosylation reaction with O-PhCar (54) and O-Poc (55) donors showing high β-selectivity [133].
Scheme 11: Neighbouring group participation rendered by an N-benzylcarbamoyl (BnCar) group [137] at the C-2 positio...
Scheme 12: Stereoselectivity obtained from glycosylation [138] with 2-O-(o-trifluoromethylbenzenesulfonyl)-protecte...
Scheme 13: (a) Plausible mechanistic pathway for glycosylation with C-2 DMTM protection [139] and (b) example of a ...
Scheme 14: Glycosylation reactions employing MOM 78, BOM 81, and NAPOM 83-protected thioglycoside donors. Reag...
Scheme 15: Plausible mechanistic pathway for alkoxymethyl-protected glycosyl donors. Path A. Expected product ...
Scheme 16: Plausible mechanistic pathway for alkoxymethyl-protected glycosyl donors [147].
Scheme 17: A. Formation of α-glycosides and B formation of β-glycosides by using chiral auxiliary neighbouring...
Scheme 18: Bimodal participation of 2-O-(o-tosylamido)benzyl (TAB) protecting group to form both α and β-isome...
Scheme 19: (a) 1,2-trans-Directing nature using C-2 cyanomethyl protection and (b) the effect of acceptors and...
Scheme 20: 1,3-Remote assistance by C-3-ester protection for gluco- and galactopyranosides to form 1,2-cis gly...
Scheme 21: 1,6-Remote assistance by C-6-ester protection for gluco- and galactopyranosides to form 1,2-cis gly...
Scheme 22: 1,4-Remote assistance by C-4-ester protection for galactopyranosides to form 1,2-cis glycosidic pro...
Scheme 23: Different products obtained on activation of axial 3-O and equatorial 3-O ester protected glycoside...
Scheme 24: The role of 3-O-protection on the stereochemistry of the produced glycoside [191].
Scheme 25: The role of 4-O-protection on the stereochemistry of the produced glycosides.
Scheme 26: Formation and subsequent stability of the bicyclic oxocarbenium intermediate formed due to remote p...
Scheme 27: The role a C-6 p-nitrobenzoyl group on the stereochemistry of the glycosylated product [196].
Scheme 28: Difference in stereoselectivity obtained in glycosylation reactions by replacing non-participating ...
Scheme 29: The role of electron-withdrawing and electron-donating substituents on the C-4 acetyl group in glyc...
Scheme 30: Effect of the introduction of a methyl group in the C-4 position on the glycosylation with more rea...
Figure 3: Remote group participation effect exhibited by the 2,2-dimethyl-2-(o-nitrophenyl)acetyl (DMNPA) pro...
Scheme 31: The different stereoselectivities obtained by Pic and Pico donors on being activated by DMTST.
Figure 4: Hydrogen bond-mediated aglycon delivery (HAD) in glycosylation reactions for 1,2-cis 198a and 1,2-t...
Scheme 32: The role of different acceptor with 6-O-Pic-protected glycosyl donors.
Scheme 33: The role of the remote C-3 protection on various 4,6-O-benzylidene-protected mannosyl donors affect...
Scheme 34: The dual contribution of the DTBS group in glycosylation reactions [246,247].
Heteroannulations of cyanoacetamide-based MCR scaffolds utilizing formamide
- Marios Zingiridis,
- Danae Papachristodoulou,
- Despoina Menegaki,
- Konstantinos G. Froudas and
- Constantinos G. Neochoritis
Beilstein J. Org. Chem. 2025, 21, 217–225, doi:10.3762/bjoc.21.13
- convergent chemistry characterized by diversity, complexity and efficiency. MCRs are compatible with C1 chemistry due to the generally great tolerance of different functional groups. They have been mostly employed in the synthesis of oxazolidinones and oxazinanones utilizing CO2 and CO [4][16][17][18][19][20
- anthranilic acid and B) access to heteroannulated pyrimidones by MCRs of suitably substituted heterocycles and formamide as C1 source. Access to the key building blocks 2–4 by employing three different nonisocyanide-based MCRs. Diversity and complexity were the essential features of our library of starting
Graphical Abstract
Figure 1: Heteroannulated pyrimidones in drug discovery: blockbuster drugs that are based on the privileged p...
Scheme 1: Strategies towards targeted adducts: A) Niementowski quinazoline synthesis utilizing anthranilic ac...
Scheme 2: Access to the key building blocks 2–4 by employing three different nonisocyanide-based MCRs. Divers...
Scheme 3: Synthesis of N-substituted thienopyrimidones 5a–e by a Gewald three-component reaction employing 2-...
Scheme 4: Synthesis of N-substituted quinolinopyrimidones 6a–e from 2-aminoindoles 3a–e and formamide as C1 s...
Scheme 5: Synthesis of N-substituted indolopyrimidones 7a–e from 2-aminoindoles 4a–e and formamide as C1 sour...
Figure 2: Representative fluorescence spectrum of compounds 5b (λex = 330 nm) and 6e (λex = 430 nm) at 0.2 M ...
Figure 3: Molecular geometry observed within the crystal structure of compound 7b (CCDC 2376493).
Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization
- Wentao Yu,
- Zhiyao Yang,
- Chengkan Yu,
- Xiaowei Li and
- Lihua Yuan
Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10
- noncovalent bonding interactions. It also confers on supramolecular assemblies with higher complexity and multilevel ordering [9][10][11], leading to a vast number of applications, for example, for use in detection and separation [12], sensing [13], photocatalysis [14], release [15], and as thermochromic and
Graphical Abstract
Scheme 1: a) Chemical structures of H-bonded macrocycles H1, H2, and guest G1, and schematic representation o...
Figure 1: ESIMS spectrum of an equimolar mixture of G1 and H1 in CHCl3/CH3CN (1:1, v/v), including calculated...
Figure 2: Stacked 1H NMR spectra (CDCl3/CD3CN 1:1, v/v, 400 MHz, 298 K) of G1 upon addition of different equi...
Figure 3: Single-crystal X-ray structure of the complex H2 ⊃ G1. a) Dimeric structure formed by cyclo[6]arami...
Figure 4: Stacked 1H NMR spectra (CDCl3/CD3CN 1:1, v/v, 400 MHz, 298 K) of G2 upon addition of different equi...
Figure 5: TEM images of a solution of H1, G2, and Zn(ClO4)2 at different concentrations (CHCl3/CH3CN 1:1, v/v...
Figure 6: Stacked 1H NMR spectra (CDCl3/CD3CN 1:1, v/v, 400 MHz, 298 K) of G2 and Zn2+ upon addition of diffe...
Figure 7: Specific viscosity of the linear supramolecular polymer in CHCl3/CH3CN (1:1, v/v, 298 K) at variabl...
Figure 8: Variable-concentration 1H NMR spectra of the supramolecular polymer: (a) 2.0 mM, (b) 4.0 mM, (c) 6....
Recent advances in organocatalytic atroposelective reactions
- Henrich Szabados and
- Radovan Šebesta
Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6
Graphical Abstract
Scheme 1: Formation of axially chiral styrenes 3 via iminium activation.
Scheme 2: Synthesis of axially chiral 2-arylquinolines 6.
Scheme 3: Atroposelective intramolecular (4 + 2) annulation leading to aryl-substituted indolines.
Scheme 4: Atroposelective formation of biaryl via twofold aldol condensation.
Scheme 5: Strategy towards diastereodivergent formation of axially chiral oligonaphthylenes.
Scheme 6: Atroposelective formation of chiral biaryls based on a Michael/Henry domino reaction.
Scheme 7: Organocatalytic Michael/aldol cascade followed by oxidative aromatization.
Scheme 8: Atroposelective formation of C(sp2)–C(sp3) axially chiral compounds.
Scheme 9: NHC-catalyzed synthesis of axially chiral styrenes 26.
Scheme 10: NHC-catalyzed synthesis of biaxial chiral pyranones.
Scheme 11: Formation of bridged biaryls with eight-membered lactones.
Scheme 12: The NHC-catalyzed (3 + 2) annulation of urazoles 37 and ynals 36.
Scheme 13: NHC-catalyzed synthesis of axially chiral 4‑aryl α‑carbolines 41.
Scheme 14: NHC-catalyzed construction of N–N-axially chiral pyrroles and indoles.
Scheme 15: NHC-catalyzed oxidative Michael–aldol cascade.
Scheme 16: NHC-catalyzed (4 + 2) annulation for the synthesis of benzothiophene-fused biaryls.
Scheme 17: NHC-catalyzed desymmetrization of N-aryl maleimides.
Scheme 18: NHC-catalyzed deracemization of biaryl hydroxy aldehydes 55a–k into axially chiral benzonitriles 56a...
Scheme 19: NHC-catalyzed desymmetrization of 2-aryloxyisophthalaldehydes.
Scheme 20: NHC-catalyzed DKR of 2-arylbenzaldehydes 62.
Scheme 21: Atroposelective biaryl amination.
Scheme 22: CPA-catalyzed atroposelective amination of 2-anilinonaphthalenes.
Scheme 23: Atroposelective DKR of naphthylindoles.
Scheme 24: CPA-catalyzed kinetic resolution of binaphthylamines.
Scheme 25: Atroposelective amination of aromatic amines with diazodicarboxylates.
Scheme 26: Atroposelective Friedländer heteroannulation.
Scheme 27: CPA-catalyzed formation of axially chiral 4-arylquinolines.
Scheme 28: CPA-catalyzed Friedländer reaction of arylketones with cyclohexanones.
Scheme 29: CPA-catalyzed atroposelective Povarov reaction.
Scheme 30: Atroposelective CPA-catalyzed Povarov reaction.
Scheme 31: Paal–Knorr formation of axially chiral N-pyrrolylindoles and N-pyrrolylpyrroles.
Scheme 32: Atroposelective Paal–Knorr reaction leading to N-pyrrolylpyrroles.
Scheme 33: Atroposelective Pictet–Spengler reaction of N-arylindoles with aldehydes.
Scheme 34: Atroposelective Pictet–Spengler reaction leading to tetrahydroisoquinolin-8-ylanilines.
Scheme 35: Atroposelective formation of arylindoles.
Scheme 36: CPA-catalyzed arylation of naphthoquinones with indolizines.
Scheme 37: Atroposelective reaction of o-naphthoquinones.
Scheme 38: CPA-catalyzed formation of axially chiral arylquinones.
Scheme 39: CPA-catalyzed axially chiral N-arylquinones.
Scheme 40: Atroposelective additions of bisindoles to isatin-based 3-indolylmethanols.
Scheme 41: CPA-catalyzed synthesis of axially chiral arylindolylindolinones.
Scheme 42: CPA-catalyzed reaction between bisindoles and ninhydrin-derived 3-indoylmethanols.
Scheme 43: Atroposelective reaction of bisindoles and isatin-derived imines.
Scheme 44: CPA-catalyzed formation of axially chiral bisindoles.
Scheme 45: Atroposelective reaction of 2-naphthols with alkynylhydroxyisoindolinones.
Scheme 46: CPA-catalyzed reaction of indolylnaphthols with propargylic alcohols.
Scheme 47: Atroposelective formation of indolylpyrroloindoles.
Scheme 48: Atroposelective reaction of indolylnaphthalenes with alkynylnaphthols.
Scheme 49: CPA-catalyzed addition of naphthols to alkynyl-2-naphthols and 2-naphthylamines.
Scheme 50: CPA-catalyzed formation of axially chiral aryl-alkene-indoles.
Scheme 51: CPA-catalyzed formation of axially chiral styrenes.
Scheme 52: Atroposelective formation of alkenylindoles.
Scheme 53: Atroposelective formation of axially chiral arylquinolines.
Scheme 54: Atroposelective (3 + 2) cycloaddition of alkynylindoles with azonaphthalenes.
Scheme 55: CPA-catalyzed formation of axially chiral 3-(1H-benzo[d]imidazol-2-yl)quinolines.
Scheme 56: Atroposelective cyclization of 3-(arylethynyl)-1H-indoles.
Scheme 57: Atroposelective three-component heteroannulation.
Scheme 58: CPA-catalyzed formation of arylbenzimidazols.
Scheme 59: CPA-catalyzed reaction of N-naphthylglycine esters with nitrosobenzenes.
Scheme 60: CPA-catalyzed formation of axially chiral N-arylbenzimidazoles.
Scheme 61: CPA-catalyzed formation of axially chiral arylbenzoindoles.
Scheme 62: CPA-catalyzed formation of pyrrolylnaphthalenes.
Scheme 63: CPA-catalyzed addition of naphthols and indoles to nitronaphthalenes.
Scheme 64: Atroposelective reaction of heterobiaryl aldehydes and aminobenzamides.
Scheme 65: Atroposelective cyclization forming N-arylquinolones.
Scheme 66: Atroposelective formation of 9H-carbazol-9-ylnaphthalenes and 1H-indol-1-ylnaphthalene.
Scheme 67: CPA-catalyzed formation of pyrazolylnaphthalenes.
Scheme 68: Atroposelective addition of diazodicarboxamides to azaborinephenols.
Scheme 69: Catalytic formation of axially chiral arylpyrroles.
Scheme 70: Atroposelective coupling of 1-azonaphthalenes with 2-naphthols.
Scheme 71: CPA-catalyzed formation of axially chiral oxindole-based styrenes.
Scheme 72: Atroposelective electrophilic bromination of aminonaphthoquinones.
Scheme 73: Atroposelective bromination of dienes.
Scheme 74: CPA-catalyzed formation of axially chiral 5-arylpyrimidines.
Scheme 75: Atroposelective hydrolysis of biaryloxazepines.
Scheme 76: Atroposelective opening of dinaphthosiloles.
Scheme 77: Atroposelective reduction of naphthylenals.
Scheme 78: Atroposelective allylic substitution with 2-naphthols.
Scheme 79: Atroposelective allylic alkylation with phosphinamides.
Scheme 80: Atroposelective allylic substitution with aminopyrroles.
Scheme 81: Atroposelective allylic substitution with aromatic sulfinamides.
Scheme 82: Atroposelective sulfonylation of naphthylynones.
Scheme 83: Squaramide-catalyzed reaction of alkynyl-2-naphthols with 5H-oxazolones.
Scheme 84: Formation of axially chiral styrenes via sulfonylative opening of cyclopropanols.
Scheme 85: Atroposelective organo-photocatalyzed sulfonylation of alkynyl-2-naphthols.
Scheme 86: Thiourea-catalyzed atroposelective cyclization of alkynylnaphthols.
Scheme 87: Squaramide-catalyzed formation of axially chiral naphthylisothiazoles.
Scheme 88: Atroposelective iodo-cyclization catalyzed by squaramide C69.
Scheme 89: Squaramide-catalyzed formation of axially chiral oligoarenes.
Scheme 90: Atroposelective ring-opening of cyclic N-sulfonylamides.
Scheme 91: Thiourea-catalyzed kinetic resolution of naphthylpyrroles.
Scheme 92: Atroposelective ring-opening of arylindole lactams.
Scheme 93: Atroposelective reaction of 1-naphthyl-2-tetralones and diarylphosphine oxides.
Scheme 94: Atroposelective reaction of iminoquinones with indoles.
Scheme 95: Kinetic resolution of binaphthylalcohols.
Scheme 96: DKR of hydroxynaphthylamides.
Scheme 97: Atroposelective N-alkylation with phase-transfer catalyst C75.
Scheme 98: Atroposelective allylic substitution via kinetic resolution of biarylsulfonamides.
Scheme 99: Atroposelective bromo-functionalization of alkynylarenes.
Scheme 100: Sulfenylation-induced atroposelective cyclization.
Scheme 101: Atroposelective O-sulfonylation of isochromenone-indoles.
Scheme 102: NHC-catalyzed atroposelective N-acylation of anilines.
Scheme 103: Peptide-catalyzed atroposelective ring-opening of lactones.
Scheme 104: Peptide-catalyzed coupling of 2-naphthols with quinones.
Scheme 105: Atroposelective nucleophilic aromatic substitution of fluoroarenes.
Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning
- Pablo Quijano Velasco,
- Kedar Hippalgaonkar and
- Balamurugan Ramalingam
Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3
- substantial resources and are labor-intensive, often exploring only a single variable in search of the optimal conditions while disregarding the intricate interactions among competing variables within the synthesis process. The complexity of the problem requires consideration that process optimization often
Graphical Abstract
Figure 1: A high-level representation of the workflow and framework used for the optimization of organic reac...
Figure 2: (a) Photograph showing a Chemspeed HTE platform using 96-well reaction blocks. (b) Mobile robot equ...
Figure 3: (a) Description of a slug flow platform developed using segments of gas as separation medium for hi...
Figure 4: Schematic representation (a) and photograph (b) of the flow parallel synthesizer intelligently desi...
Figure 5: (a) Schematic representation of an ASFR for obtaining an optimal solution with minimal human interv...
Figure 6: (a) A modular flow platform developed for a wider variety of chemical syntheses. (b) Various catego...
Figure 7: Implementation of four complementary PATs into the optimization process of a three-step synthesis.
Figure 8: Overlay of several Raman spectra of a single condition featuring the styrene vinyl region (a) and t...
Figure 9: (a) Schematic description of the process of chemical reaction optimization through ML methods. (b) ...
Figure 10: (a) Comparison between a standard GP (single-task) and a multitask GP. Training an auxiliary task u...
Figure 11: Comparison of the reaction yield between optimizations campaign where the catalyst ligand selection...
Ceratinadin G, a new psammaplysin derivative possessing a cyano group from a sponge of the genus Pseudoceratina
- Shin-ichiro Kurimoto,
- Kouta Inoue,
- Taito Ohno and
- Takaaki Kubota
Beilstein J. Org. Chem. 2024, 20, 3215–3220, doi:10.3762/bjoc.20.267
- ]undeca-2,7,9-trien-4-ol moiety classified as psammaplysin derivatives. About 50 psammaplysin derivatives have been identified so far [2][3]. Among bromotyrosine alkaloids, the psammaplysin derivatives are particularly intriguing due to their structural complexity and biological activities. Psammaplysin
Graphical Abstract
Figure 1: Structures of ceratinadin G (1) and psammaplysin F (2).
Figure 2: Selected 2D NMR correlations for ceratinadin G (1).
Figure 3: ECD spectra of ceratinadin G (1) and psammaplysin F (2) in MeOH.
Synthesis of the 1,5-disubstituted tetrazole-methanesulfonylindole hybrid system via high-order multicomponent reaction
- Cesia M. Aguilar-Morales,
- América A. Frías-López,
- Nadia V. Emilio-Velázquez,
- Alejandro Islas-Jácome,
- Angelica Judith Granados-López,
- Jorge Gustavo Araujo-Huitrado,
- Yamilé López-Hernández,
- Hiram Hernández-López,
- Luis Chacón-García,
- Jesús Adrián López and
- Carlos J. Cortés-García
Beilstein J. Org. Chem. 2024, 20, 3077–3084, doi:10.3762/bjoc.20.256
- structural diversity and complexity compared to classical 3- or 4-CRs [17][18][19]. In the same context, the hybridization of 1,5-disubstituted tetrazoles with an indole moiety using I-MCRs such as the Ugi-azide reaction as a key step, is very limited. To our knowledge, only three reactions have been
- -disubstituted tetrazole-methanesulfonylindole derivatives, with yields ranging from 16% to 55% after purification by column chromatography. Despite some yields being modest, they are deemed reasonable considering the reaction’s structural complexity, atom economy, and the efficiency achieved in terms of time
Graphical Abstract
Scheme 1: Synthetic approaches to obtain the 1,5-disubstituted tetrazole-indole system and our synthetic appr...
Scheme 2: High-order multicomponent reaction for the synthesis of 1,5-disubstituted tetrazol-methanesulfonyli...
Scheme 3: Plausible reaction mechanism for the synthesis of target molecules 18a–n.
Figure 1: Differential effect of the 1,5-disubstituted tetrazole-indole hybrid compounds 18a–j on proliferati...
Tailored charge-neutral self-assembled L2Zn2 container for taming oxalate
- David Ocklenburg and
- David Van Craen
Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250
- inevitable presence of counteranions necessary to balance the positive charge increases the complexity of the underlying equilibria. Competition between the desired guest and the counteranions can lead to significantly weakened binding strength of the target analyte in the worst case. One option to mitigate
Graphical Abstract
Figure 1: a) Generally desired guest recognition by encapsulation of the analyte within self-assembled metal-...
Scheme 1: Two-synthon approach for ligand preparation via CuAAC click reaction of an azide-functionalized, pr...
Figure 2: Recognition of mono- and dicarboxylates with [L2Zn2] which results in the formation of 1:1 host–gue...
Figure 3: a) Optimized structure (ωB97X‒D4 [83]/def2-SVP [84,85], implicit solvation with DMSO [86], ORCA 5.0.3 [81,82]) of [(C2)@L2...
Figure 4: 1H NMR competition experiments (500 MHz, 500 µM, DMSO-d6, 25 °C) with mixtures of studied analytes ...
Advances in radical peroxidation with hydroperoxides
- Oleg V. Bityukov,
- Pavel Yu. Serdyuchenko,
- Andrey S. Kirillov,
- Gennady I. Nikishin,
- Vera A. Vil’ and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249
- Kharasch–Sosnovsky peroxidation became the basic universal platform for the development of peroxidation methods, with its great potential for rapid generation of complexity due to the ability to couple the resulting free radicals with a wide range of partners. This review discusses the recent advances in
Graphical Abstract
Scheme 1: Organic peroxide initiators in polymer chemistry.
Scheme 2: Synthesis of organic peroxides.
Scheme 3: Richness of radical cascades with species formed from hydroperoxides in redox conditions.
Scheme 4: Co-catalyzed allylic peroxidation of alkenes 1 and 3 by TBHP.
Scheme 5: Allylic peroxidation of alkenes 6 by Pd(II)TBHP.
Scheme 6: Cu(I)-catalyzed allylic peroxidation.
Scheme 7: Enantioselective peroxidation of alkenes 10 with TBHP in the presence of copper(I) compounds.
Scheme 8: Oxidation of α-pinene (12) by the Cu(I)/TBHP system.
Scheme 9: Introduction of the tert-butylperoxy fragment into the α-position of cyclic ketones 15 and 17.
Scheme 10: α-Peroxidation of β-dicarbonyl compounds 19 using the Cu(II)/TBHP system.
Scheme 11: Co-catalyzed peroxidation of cyclic compounds 21 with TBHP.
Scheme 12: Co-, Mn- and Fe-catalyzed peroxidation of 2-oxoindoles 23, barbituric acids 25, and 4-hydroxycoumar...
Scheme 13: Cu-catalyzed and metal-free peroxidation of barbituric acid derivatives 31 and 3,4-dihydro-1,4-benz...
Scheme 14: Electrochemical peroxidation of 1,3-dicarbonyl compounds 35.
Scheme 15: Peroxidation of β-dicarbonyl compounds, cyanoacetic esters and malonic esters 37 by the TBAI/TBHP s...
Scheme 16: Cu-catalyzed peroxidation of malonodinitriles and cyanoacetic esters 39 with TBHP.
Scheme 17: Mn-catalyzed remote peroxidation via trifluromethylation of double bond.
Scheme 18: Cu-catalyzed remote peroxidation via trifluromethylthiolation of double bond.
Scheme 19: Fe-, Mn-, and Ru-catalyzed peroxidation of alkylaromatics 45, 47, 49, and 51 with TBHP.
Scheme 20: Cu-catalyzed peroxidation of diphenylacetonitrile (53) with TBHP.
Scheme 21: Cu-catalyzed peroxidation of benzyl cyanides 60 with TBHP.
Scheme 22: Synthesis of tert-butylperoxy esters 63 from benzyl alcohols 62 using the TBAI/TBHP system.
Scheme 23: Enantioselective peroxidation of 2-phenylbutane (64) with TBHP and chiral Cu(I) complex.
Scheme 24: Photochemical synthesis of peroxides 67 from carboxylic acids 66.
Scheme 25: Photochemical peroxidation of benzylic C(sp3)–H.
Scheme 26: Cu- and Ru-catalyzed peroxidation of alkylamines with TBHP.
Scheme 27: Peroxidation of amides 76 with the TBAI/TBHP system.
Scheme 28: Fe-catalyzed functionalization of ethers 78 with TBHP.
Scheme 29: Synthesis of 4-(tert-butylperoxy)-5-phenyloxazol-2(3H)-ones 82 from benzyl alcohols 80 and isocyana...
Scheme 30: Fe- and Co-catalyzed peroxidation of alkanes with TBHP.
Scheme 31: Rh-catalyzed tert-butylperoxy dienone synthesis with TBHP.
Scheme 32: Rh- and Cu-catalyzed phenolic oxidation with TBHP.
Scheme 33: Metal-free peroxidation of phenols 94.
Scheme 34: Cu-catalyzed alkylation–peroxidation of acrylonitrile.
Scheme 35: Cu-catalyzed cycloalkylation–peroxidation of coumarins 99.
Scheme 36: Metal-free cycloalkylation–peroxidation of coumarins 102.
Scheme 37: Difunctionalization of indene 104 with tert-butylperoxy and alkyl groups.
Scheme 38: Acid-catalyzed radical addition of ketones (108, 111) and TBHP to alkenes 107 and acrylates 110.
Scheme 39: Cu-catalyzed alkylation–peroxidation of alkenes 113 with TBHP and diazo compounds 114.
Scheme 40: Cobalt(II)-catalyzed addition of TBHP and 1,3-dicarbonyl compound 116 to alkenes 117.
Scheme 41: Cu(0)- or Co(II)-catalyzed addition of TBHP and alcohols 120 to alkenes 119.
Scheme 42: Fe-catalyzed functionalization of allenes 122 with TBHP.
Scheme 43: Fe-catalyzed alkylation–peroxidation of alkenes 125 and 127.
Scheme 44: Fe- and Co-catalyzed alkylation–peroxidation of alkenes 130, 133 and 134 with TBHP and aldehydes as...
Scheme 45: Carbonylation–peroxidation of alkenes 137, 140, 143 with hydroperoxides and aldehydes.
Scheme 46: Carbamoylation–peroxidation of alkenes 146 with formamides and TBHP.
Scheme 47: TBAB-catalyzed carbonylation–peroxidation of alkenes.
Scheme 48: VOCl2-catalyzed carbonylation–peroxidation of alkenes 152.
Scheme 49: Acylation–peroxidation of alkenes 155 with aldehydes 156 and TBHP using photocatalysis.
Scheme 50: Cu-catalyzed peroxidation of styrenes 158.
Scheme 51: Fe-catalyzed acylation-peroxidation of alkenes 161 with carbazates 160 and TBHP.
Scheme 52: Difunctionalization of alkenes 163, 166 with TBHP and (per)fluoroalkyl halides.
Scheme 53: Difunctionalization of alkenes 169 and 172 with hydroperoxides and sodium (per)fluoromethyl sulfina...
Scheme 54: Trifluoromethylation–peroxidation of styrenes 175 using MOF Cu3(BTC)2 as a catalyst.
Scheme 55: Difunctionalization of alkenes 178 with tert-butylperoxy and dihalomethyl fragments.
Scheme 56: Difunctionalization of alkenes 180 with the tert-butylperoxy and dihalomethyl moieties.
Scheme 57: The nitration–peroxidation of alkenes 182 with t-BuONO and TBHP.
Scheme 58: Azidation–peroxidation of alkenes 184 with TMSN3 and TBHP.
Scheme 59: Co-catalyzed bisperoxidation of butadiene 186.
Scheme 60: Bisperoxidation of styrene (189) and acrylonitrile (192) with TBHP by Minisci.
Scheme 61: Mn-catalyzed synthesis of bis(tert-butyl)peroxides 195 from styrenes 194.
Scheme 62: Bisperoxidation of arylidene-9H-fluorenes 196 and 3-arylidene-2-oxoindoles 198 with TBHP under Mn-c...
Scheme 63: Synthesis of bisperoxides from styrenes 200 and 203 using the Ru and Rh catalysis.
Scheme 64: Iodine-catalyzed bisperoxidation of styrenes 206.
Scheme 65: Synthesis of di-tert-butylperoxyoxoindoles 210 from acrylic acid anilides 209 using a Pd(II)/TBHP o...
Scheme 66: Pinolation/peroxidation of styrenes 211 catalyzed by Cu(I).
Scheme 67: TBAI-catalyzed acyloxylation–peroxidation of alkenes 214 with carboxylic acids and TBHP.
Scheme 68: Difunctionalization of alkenes 217 with TBHP and water or alcohols.
Scheme 69: TBAI-catalyzed hydroxyperoxidation of 1,3-dienes 220.
Scheme 70: Hydroxyperoxidation of 1,3-dienes 220.
Scheme 71: Iodination/peroxidation of alkenes 223 with I2 and hydroperoxides.
Scheme 72: The reactions of cyclic enol ethers 226 and 228 with I2/ROOH system.
Scheme 73: Synthesis of 1-(tert-butylperoxy)-2-iodoethanes 231.
Scheme 74: Synthesis of 1-iodo-2-(tert-butylperoxy)ethanes 233.
Scheme 75: Cu-catalyzed phosphorylation–peroxidation of alkenes 234.
Scheme 76: Co-catalyzed phosphorylation–peroxidation of alkenes 237.
Scheme 77: Ag-catalyzed sulfonylation–peroxidation of alkenes 241.
Scheme 78: Co-catalyzed sulfonylation–peroxidation of alkenes 244.
Scheme 79: Synthesis of α/β-peroxysulfides 248 and 249 from styrenes 247.
Scheme 80: Cu-catalyzed trifluoromethylthiolation–peroxidation of alkenes 250 and allenes 252.
Scheme 81: Photocatalytic sulfonyl peroxidation of alkenes 254 via deamination of N-sulfonyl ketimines 255.
Scheme 82: Photoredox-catalyzed 1,4-peroxidation–sulfonylation of enynones 257.
Scheme 83: Cu-catalyzed silylperoxidation of α,β-unsaturated compounds 260 and enynes 261.
Scheme 84: Fe-catalyzed silyl peroxidation of alkenes.
Scheme 85: Cu-catalyzed germyl peroxidation of alkenes 267.
Scheme 86: TBAI-catalyzed intramolecular cyclization of diazo compounds 269 with further peroxidation.
Scheme 87: Co-catalyzed three-component coupling of benzamides 271, diazo compounds 272 and TBHP.
Scheme 88: Co-catalyzed esterification-peroxidation of diazo compounds 274 with TBHP and carboxylic acids 275.
Scheme 89: Cu-catalyzed alkylation–peroxidation of α-carbonylimines 277 or ketones 280.
Scheme 90: Mn-catalyzed ring-opening peroxidation of cyclobutanols 282 with TBHP.
Scheme 91: Peroxycyclization of tryptamines 284 with TBHP.
Scheme 92: Radical cyclization–peroxidation of homotryptamines 287.
Scheme 93: Iodine-catalyzed oxidative coupling of indoles 288, cyanoacetic esters and TBHP.
Scheme 94: Summary of metal-catalyzed peroxidation processes.
