Search for "radical addition" in Full Text gives 127 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101
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.
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.
Beilstein J. Org. Chem. 2025, 21, 1024–1030, doi:10.3762/bjoc.21.84
Graphical Abstract
Scheme 1: a) CDs-mediated 1,2-difunctionalization of alkenes by alkyl halides R–Y and b) light-driven reducti...
Figure 1: UV–vis spectra of the CDs. All the measurements have been performed in water, except for CD-a-GLU, ...
Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76
Graphical Abstract
Figure 1: D–A–D organic PCs previously reported and our new D–A bimodal organic PCs.
Figure 2: Selected frontier MOs and relative calculated energies of D–A photocatalysts (4a,5a–e, and 6a). Abs...
Figure 3: Comparison of the ground state redox potential of the acceptor moieties (4–6), the donor moieties (a...
Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73
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].
Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61
Graphical Abstract
Scheme 1: Electrosynthesis of phenanthridine phosphine oxides.
Scheme 2: Electrosynthesis of 1-aminoalkylphosphine oxides.
Scheme 3: Various electrochemical C–P coupling reactions.
Scheme 4: Electrochemical C–P coupling reaction of indolines.
Scheme 5: Electrochemical C–P coupling reaction of ferrocene.
Scheme 6: Electrochemical C–P coupling reaction of acridines with phosphites.
Scheme 7: Electrochemical C–P coupling reaction of alkenes.
Scheme 8: Electrochemical C–P coupling reaction of arenes in a flow system.
Scheme 9: Electrochemical C–P coupling reaction of heteroarenes.
Scheme 10: Electrochemical C–P coupling reaction of thiazoles.
Scheme 11: Electrochemical C–P coupling reaction of indole derivatives.
Scheme 12: Electrosynthesis of 1-amino phosphonates.
Scheme 13: Electrochemical C–P coupling reaction of aryl and vinyl bromides.
Scheme 14: Electrochemical C–P coupling reaction of phenylpyridine with dialkyl phosphonates in the presence o...
Scheme 15: Electrochemical P–C bond formation of amides.
Scheme 16: Electrochemical synthesis of α-hydroxy phosphine oxides.
Scheme 17: Electrochemical synthesis of π-conjugated phosphonium salts.
Scheme 18: Electrochemical phosphorylation of indoles.
Scheme 19: Electrochemical synthesis of phosphorylated propargyl alcohols.
Scheme 20: Electrochemical synthesis of phosphoramidates.
Scheme 21: Electrochemical reaction of carbazole with diphenylphosphine.
Scheme 22: Electrochemical P–N coupling of carbazole with phosphine oxides.
Scheme 23: Electrochemical P–N coupling of indoles with a trialkyl phosphite.
Scheme 24: Electrochemical synthesis of iminophosphoranes.
Scheme 25: Electrochemical P–O coupling of phenols with dialkyl phosphonate.
Scheme 26: Electrochemical P–O coupling of alcohols with diphenylphosphine.
Scheme 27: Electrochemical P–S coupling of thiols with dialkylphosphines.
Scheme 28: Electrochemical thiophosphorylation of indolizines.
Scheme 29: Electrosynthesis of S-heteroaryl phosphorothioates.
Scheme 30: Electrochemical phosphorylation reactions.
Scheme 31: Electrochemical P–Se formation.
Scheme 32: Electrochemical selenation/halogenation of alkynyl phosphonates.
Scheme 33: Electrochemical enantioselective aryl C–H bond activation.
Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33
Graphical Abstract
Figure 1: The Grotthuss–Draper, Einstein–Stark, and Beer–Lambert laws. T: transmittance; ε: molar attenuation...
Figure 2: The benefits of merging photochemistry with mechanochemical setups (top). Most common setups for ph...
Scheme 1: Mechanochemically triggered pedal-like motion in solid-state [2 + 2] photochemical cycloaddition fo...
Scheme 2: Mechanically promoted [2 + 2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene (2.1) via supra...
Scheme 3: Photo-thermo-mechanosynthesis of quinolines [65].
Scheme 4: Study of the mechanically assisted [2 + 2] photodimerization of chalcone [66].
Scheme 5: Liquid-assisted vortex grinding (LAVG) for the synthesis of [2.2]paracyclophane [68].
Scheme 6: Photomechanochemical approach for the riboflavin tetraacetate-catalyzed photocatalytic oxidation of...
Scheme 7: Photomechanochemical oxidation of 1,2-diphenylethyne to benzil. The photo in Scheme 7 was republished with ...
Scheme 8: Photomechanochemical borylation of aryldiazonium salts. The photo in Scheme 8 was reproduced from [72] (© 2017 ...
Scheme 9: Photomechanochemical control over stereoselectivity in the [2 + 2] dimerization of acenaphthylene. ...
Scheme 10: Photomechanochemical synthesis of polyaromatic compounds using UV light. The photo in Scheme 10 was reproduc...
Scheme 11: Mechanically assisted photocatalytic reactions: A) atom-transfer-radical addition, B) pinacol coupl...
Scheme 12: Use of mechanoluminescent materials as photon sources for photomechanochemistry. SAOED: SrAl2O4:Eu2+...
Figure 3: SWOT (strengths, weaknesses, opportunities, threats) analysis of photomechanochemistry.
Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22
Graphical Abstract
Figure 1: Influence of the metal center M (Fe, Ru, Os) on the position of the MLCT and MC (metal-centered) ab...
Scheme 1: Red-light-mediated ring-closing metathesis through activation of a ruthenium catalyst by an osmium ...
Scheme 2: Photocatalyzed polymerization of dicylopentadiene mediated with red or blue light.
Figure 2: Comparison between [Ru(bpy)3]2+ and [Os(tpy)2]2+ in a photocatalyzed trifluoromethylation reaction:...
Scheme 3: Red-light photocatalyzed C–N cross-coupling reaction by T. Rovis et al. (SET = single-electron tran...
Figure 3: Red-light-mediated aryl oxidative addition with a bismuthinidene complex.
Scheme 4: Red-light-mediated reduction of aryl derivatives by O. S. Wenger et al. (PC = photocatalyst, anh = ...
Scheme 5: Red-light-mediated aryl halides reduction with an isoelectronic chromium complex (TDAE = tetrakis(d...
Scheme 6: Red-light-photocatalyzed trifluoromethylation of styrene derivatives with Umemoto’s reagent and a p...
Scheme 7: Red-light-mediated energy transfer for the cross-dehydrogenative coupling of N-phenyltetrahydroisoq...
Scheme 8: Red-light-mediated oxidative cyanation of tertiary amines with a phthalocyanin zinc complex.
Scheme 9: Formation of dialins and tetralins via a red-light-photocatalyzed reductive decarboxylation mediate...
Scheme 10: Oxidation of β-citronellol (28) via energy transfer mediated by a red-light activable silicon phtha...
Scheme 11: Formation of alcohol derivatives 32 from boron compounds 31 using chlorophyll (chl) as a red-light-...
Scheme 12: Red-light-driven reductive dehalogenation of α-halo ketones mediated by a thiaporphyrin photocataly...
Figure 4: Photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization medi...
Figure 5: Recent examples of red-light-mediated photocatalytic reactions with traditional organic dyes.
Figure 6: Squaraine photocatalysts used by Goddard et al. and aza-Henry reaction with squaraine-based photoca...
Figure 7: Reactions described by Goddard et al. involving 40 as the photocatalyst.
Figure 8: Various structures of squaraine derivatives used to initiate photopolymerizations.
Figure 9: Naturally occurring cyanins.
Figure 10: Influence of the structure on the photophysical properties of a cyanin dye.
Figure 11: NIR-light-mediated aza-Henry reaction photocatalyzed by 46.
Scheme 13: Photocatalyzed arylboronic acids oxidation by 46.
Figure 12: Cyanin structures synthetized and characterized by Goddard et al. (redox potentials given against s...
Figure 13: N,N′-Di-n-propyl-1,13-dimethoxyquinacridinium (55) with its redox potentials at its ground state an...
Scheme 14: Dual catalyzed C(sp2)–H arylation of 57 using DMQA 55 as the red-light-absorbing photocatalyst.
Scheme 15: Red-light-mediated aerobic oxidation of arylboronic acids 59 into phenols 60 via the use of DMQA as...
Figure 14: Red-light-photocatalyzed reactions proposed by Gianetti et al. using DMQA as the photocatalyst.
Scheme 16: Simultaneous release of NO and production of superoxide (O2•−) and their combination yielding the p...
Figure 15: Palladium porphyrin complex as the photoredox catalyst and the NO releasing substrate are linked in...
Scheme 17: Uncaging of compound 69 which is a microtubule depolymerizing agent using near IR irradiation. The ...
Scheme 18: Photochemical uncaging of drugs protected with a phenylboronic acid derivative using near IR irradi...
Scheme 19: Photoredox catalytical generation of aminyl radicals with near IR irradiation for the transfer of b...
Scheme 20: Photoredox catalytical fluoroalkylation of tryptophan moieties.
Figure 16: Simultaneous absorption of two photons of infrared light of low energy enables electronic excitatio...
Scheme 21: Uncaging Ca2+ ions using two-photon excitation with near infrared light.
Beilstein J. Org. Chem. 2025, 21, 155–178, doi:10.3762/bjoc.21.9
Graphical Abstract
Figure 1: General mechanisms of traditional and radical-mediated cross-coupling reactions.
Figure 2: Types of electrocatalysis (using anodic oxidation).
Figure 3: Recent developments and features of electrochemical copper catalysis.
Figure 4: Scheme and proposed mechanism for Cu-catalyzed alkynylation and annulation of benzamide.
Figure 5: Scheme and proposed mechanism for Cu-catalyzed asymmetric C–H alkynylation.
Figure 6: Scheme for Cu/TEMPO-catalyzed C–H alkenylation of THIQs.
Figure 7: Scheme and proposed mechanism for Cu-catalyzed electrophotochemical enantioselective cyanation of b...
Figure 8: Scheme and proposed mechanism for Cu-catalyzed electrophotochemical asymmetric heteroarylcyanation ...
Figure 9: Scheme and proposed mechanism for Cu-catalyzed enantioselective regiodivergent cross-dehydrogenativ...
Figure 10: Scheme and proposed mechanism for Cu/Ni-catalyzed stereodivergent homocoupling of benzoxazolyl acet...
Figure 11: Scheme and proposed mechanism for Cu-catalyzed electrochemical amination.
Figure 12: Scheme and proposed mechanism for Cu-catalyzed electrochemical azidation of N-arylenamines and annu...
Figure 13: Scheme and proposed mechanism for Cu-catalyzed electrochemical halogenation.
Figure 14: Scheme and proposed mechanism for Cu-catalyzed asymmetric cyanophosphinoylation of vinylarenes.
Figure 15: Scheme and proposed mechanism for Cu/Co dual-catalyzed asymmetric hydrocyanation of alkenes.
Figure 16: Scheme and proposed mechanism for Cu-catalyzed electrochemical diazidation of olefins.
Figure 17: Scheme and proposed mechanism for Cu-catalyzed electrochemical azidocyanation of alkenes.
Figure 18: Scheme and proposed mechanism for Cu-catalyzed electrophotochemical asymmetric decarboxylative cyan...
Figure 19: Scheme and proposed mechanism for electrocatalytic Chan–Lam coupling.
Beilstein J. Org. Chem. 2024, 20, 3274–3280, doi:10.3762/bjoc.20.271
Graphical Abstract
Figure 1: Giese reaction: Radical addition on olefins with an electron-withdrawing group (EWG) followed by a ...
Figure 2: Alkyl bromide and Dha derivative scope. Reaction conditions: Dha derivative (0.5 mmol), alkyl bromi...
Figure 3: Scaled-up reaction. Reaction conditions: Dha derivative (2.2 mmol), alkyl bromide (5.4 mmol), tris(...
Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259
Graphical Abstract
Figure 1: (Top) highlighting selectivity challenges in the synthesis of [n]staffanes using excess [1.1.1]prop...
Figure 2: Computed free energy profile for the oligomerization of [1.1.1]propellane (1) following SF5 radical...
Figure 3: Computed free energy profile for the oligomerization of [1.1.1]propellane (1) following CF3SF4 radi...
Figure 4: (A) The molecular structure of 3 at 90 K with 5 independent moieties in the asymmetric axis viewed ...
Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249
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.
Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214
Graphical Abstract
Figure 1: Classification of LSF reactions in this review.
Scheme 1: C(sp2)–H trifluoromethylation of heteroarenes.
Scheme 2: C(sp2)–H and C(sp3)–H alkylation of complex molecules.
Scheme 3: Electrochemical oxidation-induced intermolecular aromatic C–H sulfonamidation.
Scheme 4: Bioconjugation of tyrosine with (a) phenothiazine and (b) urazole derivatives.
Scheme 5: Electrochemical iodoamination of indoles using unactivated amines.
Scheme 6: Allylic C(sp3)–H aminations with sulfonamides.
Scheme 7: Electrochemical benzylic oxidation of C–H bonds.
Scheme 8: Site-selective electrooxidation of methylarenes to aromatic acetals.
Scheme 9: Electrochemical activation of C–H by electron-deficient W2C nanocrystals.
Scheme 10: α-Acyloxy sulfide preparation via C–H/OH cross-dehydrogenative coupling.
Scheme 11: Aromatic C–H-bond thiolation.
Scheme 12: C(sp2)–H functionalization for the installation of sulfonamide groups.
Scheme 13: Preparation of (hetero)aryl chlorides and vinyl chloride with 1,2-dichloroethane. aCu(OAc)2 (0.05 e...
Scheme 14: Electrochemical dual-oxidation enables access to α-chlorosulfoxides.
Scheme 15: Regio- and chemoselective formyloxylation–bromination/chlorination/trifluoromethylation of alkenes.
Scheme 16: Aziridine formation by coupling amines and alkenes.
Scheme 17: Formation of iminosulfide ethers via difunctionalization of an isocyanide.
Scheme 18: Synthesis of 1,3-difunctionalized molecules via C–C-bond cleavage of arylcyclopropane.
Scheme 19: Electrooxidative amino- and oxyselenation of alkenes. VBImBr = 1-butyl-3-vinylimidazolium bromide.
Scheme 20: Electrooxidative dehydrogenative [4 + 2] annulation of indole derivatives.
Scheme 21: Electrochemical cyclization combined with alkoxylation of triticonazole.
Scheme 22: Electrochemically tuned oxidative [4 + 2] annulation of olefins with hydroxamic acids.
Scheme 23: Electrosynthesis of indole derivatives via cyclization of 2-ethynylanilines.
Scheme 24: Allylic C–H oxidation of mono-, di-, and sesquiterpenes.
Scheme 25: Oxidation of unactivated C–H bonds.
Scheme 26: Fluorination of C(sp3)–H bonds. rAP = rapid alternating polarity.
Scheme 27: C(sp3)–H α-cyanation of secondary piperidines.
Scheme 28: Selective electrochemical hydrolysis of hydrosilanes to silanols.
Scheme 29: Organocatalytic electrochemical amination of benzylic C–H bonds.
Scheme 30: Iodide ion-initiated anodic oxidation reactions.
Scheme 31: Mn(III/IV) electro-catalyzed C(sp3)–H azidation.
Scheme 32: Tailored cobalt–salen complexes enable electrocatalytic intramolecular allylic C–H functionalizatio...
Scheme 33: Cobalt–salen complexes-induced electrochemical (cyclo)additions.
Scheme 34: Electrochemical 1,2-diarylation of alkenes enabled by direct dual C–H functionalization of electron...
Scheme 35: Cobalt-electrocatalyzed atroposelective C–H annulation.
Scheme 36: Nickel-electrocatalyzed C(sp2)–H alkoxylation with secondary alcohols.
Scheme 37: Nickel-catalyzed electrochemical enantioselective amination.
Scheme 38: Ruthenium-electrocatalyzed C(sp2)–H mono- and diacetoxylation.
Scheme 39: Rhodium(III)-catalyzed aryl-C–H phosphorylation enabled by anodic oxidation-induced reductive elimi...
Scheme 40: Asymmetric Lewis-acid catalysis for the synthesis of non-racemic 1,4-dicarbonyl compounds.
Scheme 41: Electrochemical enantioselective C(sp3)–H alkenylation.
Scheme 42: Palladium-catalyzed electrochemical dehydrogenative cross-coupling.
Scheme 43: Ir-electrocatalyzed vinylic C(sp2)–H activation for the annulation between acrylic acids and alkyne...
Scheme 44: Electrochemical gold-catalyzed C(sp3)–C(sp) coupling of alkynes and arylhydrazines.
Scheme 45: Photoelectrochemical alkylation of C–H heteroarenes using organotrifluoroborates.
Scheme 46: Mn-catalyzed photoelectro C(sp3)–H azidation.
Scheme 47: Photoelectrochemical undirected C–H trifluoromethylations of (Het)arenes.
Scheme 48: Photoelectrochemical dehydrogenative cross-coupling of heteroarenes with aliphatic C–H bonds.
Scheme 49: C–H amination via photoelectrochemical Ritter-type reaction.
Scheme 50: Photoelectrochemical multiple oxygenation of C–H bonds.
Scheme 51: Accelerated C(sp3)–H heteroarylations by the f-EPC system.
Scheme 52: Photoelectrochemical cross-coupling of amines.
Scheme 53: Birch electroreduction of arenes. GSW = galvanized steel wire.
Scheme 54: Electroreductive deuterations.
Scheme 55: Chemoselective electrosynthesis using rapid alternating polarity.
Scheme 56: Electroreductive olefin–ketone coupling.
Scheme 57: Electroreductive approach to radical silylation.
Scheme 58: Electrochemical borylation of alkyl halides. CC = carbon close.
Scheme 59: Radical fluoroalkylation of alkenes.
Scheme 60: Electrochemical defluorinative hydrogenation/carboxylation.
Scheme 61: Electrochemical decarboxylative olefination.
Scheme 62: Electrochemical decarboxylative Nozaki–Hiyama–Kishi coupling.
Scheme 63: Nickel-catalyzed electrochemical reductive relay cross-coupling.
Scheme 64: Electrochemical chemo- and regioselective difunctionalization of 1,3-enynes.
Scheme 65: Electrocatalytic doubly decarboxylative crosscoupling.
Scheme 66: Electrocatalytic decarboxylative crosscoupling with aryl halides.
Scheme 67: Nickel-catalyzed electrochemical reductive coupling of halides.
Scheme 68: Nickel-electrocatalyzed enantioselective carboxylation with CO2.
Scheme 69: Reductive electrophotocatalysis for borylation.
Scheme 70: Electromediated photoredox catalysis for selective C(sp3)–O cleavages of phosphinated alcohols to c...
Scheme 71: Stereoselective electro-2-deoxyglycosylation from glycals. MFE = methyl nonafluorobutyl ether.
Scheme 72: Electrochemical peptide modifications.
Scheme 73: Electrochemical α-deuteration of amides.
Scheme 74: Electrochemical synthesis of gem-diselenides.
Scheme 75: Site-selective electrochemical aromatic C–H amination.
Scheme 76: Electrochemical coupling of heteroarenes with heteroaryl phosphonium salts.
Scheme 77: Redox-neutral strategy for the dehydroxyarylation reaction.
Scheme 78: Nickel-catalyzed electrochemical C(sp3)–C(sp2) cross-coupling of benzyl trifluoroborate and halides....
Scheme 79: Paired electrocatalysis for C(sp3)–C(sp2) coupling.
Scheme 80: Redox-neutral strategy for amination of aryl bromides.
Scheme 81: Redox-neutral cross-coupling of aryl halides with weak N-nucleophiles. aProtocol with (+) RVC | RVC...
Scheme 82: Nickel-catalyzed N-arylation of NH-sulfoximines with aryl halides.
Scheme 83: Esterification of carboxylic acids with aryl halides.
Scheme 84: Electrochemically promoted nickel-catalyzed carbon–sulfur-bond formation. GFE = graphite felt elect...
Scheme 85: Electrochemical deoxygenative thiolation by Ni-catalysis. GFE = graphite felt electrode; NFE = nick...
Scheme 86: Electrochemical coupling of peptides with aryl halides.
Scheme 87: Paired electrolysis for the phosphorylation of aryl halides. GFE = graphite felt electrode, FNE = f...
Scheme 88: Redox-neutral alkoxyhalogenation of alkenes.
Beilstein J. Org. Chem. 2024, 20, 2461–2468, doi:10.3762/bjoc.20.210
Graphical Abstract
Figure 1: A) Photoredox amidocyclization reaction. B) The strongly oxidizing Fukuzumi catalyst (I) used in th...
Figure 2: A) Access of clavam derivatives by intramolecular photoredox reaction of alkenes. B) Clavulanic aci...
Scheme 1: Preparation of alkenyl β-lactam derivatives for the intramolecular photoredox reaction.
Scheme 2: Photoredox-catalyzed intramolecular N-alkylation reactions of various β-lactams. The trans/cis dr w...
Scheme 3: Synthesis of the model substrate 14 and its photoredox-catalyzed intramolecular N-alkylation reacti...
Figure 3: Tentative mechanism for the photo-cyclization reaction.
Beilstein J. Org. Chem. 2024, 20, 2114–2128, doi:10.3762/bjoc.20.182
Graphical Abstract
Figure 1: Resonance structures and reactivity of carbon monoxide.
Figure 2: Resonance structures and reactivity of isocyanides.
Scheme 1: Possible three pathways of the E• formation for imidoylation.
Scheme 2: Radical addition of thiols to isocyanides.
Scheme 3: Selective thioselenation and catalytic dithiolation of isocyanides.
Scheme 4: Synthesis of carbacephem framework.
Scheme 5: Sequential addition of (PhSe)2 to ethyl propiolate and isocyanide.
Scheme 6: Isocyanide insertion reaction into carbon-tellurium bonds.
Scheme 7: Radical addition to isocyanides with disubstituted phosphines.
Scheme 8: Radical addition to phenyl isocyanides with diphosphines.
Scheme 9: Radical reaction of tin hydride and hydrosilane toward isocyanide.
Scheme 10: Isocyanide insertion into boron compounds.
Scheme 11: Isocyanide insertion into cyclic compounds containing boron units.
Scheme 12: Photoinduced hydrodefunctionalization of isocyanides.
Scheme 13: Tin hydride-mediated indole synthesis and cross-coupling.
Scheme 14: 2-Thioethanol-mediated radical cyclization of alkenyl isocyanide.
Scheme 15: Thiol-mediated radical cyclization of o-alkenylaryl isocyanide.
Scheme 16: (PhTe)2-assisted dithiolative cyclization of o-alkenylaryl isocyanide.
Scheme 17: Trapping imidoyl radicals with heteroatom moieties.
Scheme 18: Trapping imidoyl radicals with isocyano group.
Scheme 19: Quinoline synthesis via aza-Bergman cyclization.
Scheme 20: Phenanthridine synthesis via radical cyclization of 2-isocyanobiaryls.
Scheme 21: Phenanthridine synthesis by radical reactions with AIBN, DBP and TTMSS.
Scheme 22: Phenanthridine synthesis by oxidative cyclization of 2-isocyanobiaryls.
Scheme 23: Phenanthridine synthesis using a photoredox system.
Scheme 24: Phenanthridine synthesis induced by phosphorus-centered radicals.
Scheme 25: Phenanthridine synthesis induced by sulfur-centered radicals.
Scheme 26: Phenanthridine synthesis induced by boron-centered radicals.
Scheme 27: Phenanthridine synthesis by oxidative cyclization of 2-aminobiaryls.
Beilstein J. Org. Chem. 2024, 20, 1973–1980, doi:10.3762/bjoc.20.173
Graphical Abstract
Scheme 1: (a) Sequential π-Lewis acidic metal-catalyzed cyclization/photochemical radical addition for the fo...
Scheme 2: The reaction with benzyltrimethylsilane derivatives 2. aFlow rate was 6 mL/h and premixing zone was...
Beilstein J. Org. Chem. 2024, 20, 1967–1972, doi:10.3762/bjoc.20.172
Graphical Abstract
Figure 1: Reactivities of norcorroles with various reagents.
Scheme 1: Reaction of norcorrole 1 with AIBN.
Figure 2: Top and side views of the X-ray structures of a) 2a and b) 1 [2]. Mesityl groups and hydrogen atoms we...
Scheme 2: Reaction of norcorrole 1 with V-40.
Figure 3: UV–vis–NIR absorption spectra of 1 and 2a in CH2Cl2.
Figure 4: Cyclic voltammogram of 2a in CH2Cl2. Supporting electrolyte: 0.1 M Bu4NPF6; working electrode: glas...
Scheme 3: Plausible reaction mechanism.
Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171
Graphical Abstract
Scheme 1: 1,2-Difluoroethylene synthesis from HFO-1123.
Scheme 2: 1,2-Difluoroethylene synthesis from CFC-112 and HCFC-132.
Scheme 3: 1,2-Difluoroethylene synthesis from HFC-143.
Scheme 4: 1,2-Difluoroethylene synthesis from HCFC-142 via HCFC-142a.
Scheme 5: 1,2-Difluoroethylene synthesis from CFO-1112.
Scheme 6: 1,2-Difluoroethylene synthesis from 1,2-dichloroethylene.
Scheme 7: 1,2-Difluoroethylene synthesis from perfluoropropyl vinyl ether.
Scheme 8: Deuteration reaction of 1,2-difluoroethylene.
Scheme 9: Halogen addition to 1,2-difluoroethylene.
Scheme 10: Hypohalite addition to 1,2-difluoroethylene.
Scheme 11: N-Bromobis(trifluoromethyl)amine addition to 1,2-difluoroethylene.
Scheme 12: N-Chloroimidobis(sulfonyl fluoride) addition to 1,2-difluoroethylene.
Scheme 13: Trichlorosilane addition to 1,2-difluoroethylene.
Scheme 14: SF5Br addition to 1,2-difluoroethylene.
Scheme 15: PCl3/O2 addition to 1,2-difluoroethylene.
Scheme 16: Reaction of tetramethyldiarsine with 1,2-difluoroethylene.
Scheme 17: Reaction of trichlorofluoromethane with 1,2-difluoroethylene.
Scheme 18: Addition of perfluoroalkyl iodides to 1,2-difluoroethylene.
Scheme 19: Cyclopropanation of 1,2-difluoroethylene.
Scheme 20: Diels–Alder reaction of 1,2-difluoroethylene and hexachlorocyclopentadiene.
Scheme 21: Cycloaddition reaction of 1,2-difluoroethylene and fluorinated ketones.
Scheme 22: Cycloaddition reaction of 1,2-difluoroethylene and perfluorinated aldehydes.
Scheme 23: Photochemical cycloaddition of 1,2-difluoroethylene and hexafluorodiacetyl.
Scheme 24: Reaction of 1,2-difluoroethylene with difluorosilylene.
Scheme 25: Reaction of 1,2-difluoroethylene with aryl iodides.
Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72
Graphical Abstract
Scheme 1: Classes of hydrochlorination reactions discussed in this review.
Figure 1: Mayr’s nucleophilicity parameters for several alkenes. References for each compound can be consulte...
Figure 2: Hydride affinities relating to the reactivity of the corresponding alkene towards hydrochlorination....
Scheme 2: Distinction of polar hydrochlorination reactions.
Scheme 3: Reactions of styrenes with HCl gas or HCl solutions.
Figure 3: Normal temperature dependence for the hydrochlorination of (Z)-but-2-ene.
Figure 4: Pentane slows down the hydrochlorination of 11.
Scheme 4: Recently reported hydrochlorinations of styrenes with HCl gas or HCl solutions.
Scheme 5: Hydrochlorination reactions with di- and trisubstituted alkenes.
Scheme 6: Hydrochlorination of fatty acids with liquified HCl.
Scheme 7: Hydrochlorination with HCl/DMPU solutions.
Scheme 8: Hydrochlorination with HCl generated from EtOH and AcCl.
Scheme 9: Hydrochlorination with HCl generated from H2O and TMSCl.
Scheme 10: Regioisomeric mixtures of chlorooctanes as a result of hydride shifts.
Scheme 11: Regioisomeric mixtures of products as a result of methyl shifts.
Scheme 12: Applications of the Kropp procedure on a preparative scale.
Scheme 13: Curious example of polar anti-Markovnikov hydrochlorination.
Scheme 14: Unexpected and expected hydrochlorinations with AlCl3.
Figure 5: Ex situ-generated HCl gas and in situ application for the hydrochlorination of activated alkenes (*...
Scheme 15: HCl generated by Grob fragmentation of 92.
Scheme 16: Formation of chlorophosphonium complex 104 and the reaction thereof with H2O.
Scheme 17: Snyder’s hydrochlorination with stoichiometric amounts of complex 104 or 108.
Scheme 18: In situ generation of HCl by mixing of MsOH with CaCl2.
Scheme 19: First hydrochlorination of alkenes using hydrochloric acid.
Scheme 20: Visible-light-promoted hydrochlorination.
Scheme 21: Silica gel-promoted hydrochlorination of alkenes with hydrochloric acid.
Scheme 22: Hydrochlorination with hydrochloric acid promoted by acetic acid or iron trichloride.
Figure 6: Metal hydride hydrogen atom transfer reactions vs cationic reactions; BDE (bond-dissociation energy...
Scheme 23: Carreira’s first report on radical hydrochlorinations of alkenes.
Figure 7: Mechanism for the cobalt hydride hydrogen atom transfer reaction reported by Carreira.
Scheme 24: Radical “hydrogenation” of alkenes; competing chlorination reactions.
Scheme 25: Bogers iron-catalyzed radical hydrochlorination.
Scheme 26: Hydrochlorination instead of hydrogenation product.
Scheme 27: Optimization of the Boger protocol by researchers from Merck [88,89].
Figure 8: Proposed mechanism for anti-Markovnikov hydrochlorination by Nicewicz.
Scheme 28: anti-Markovnikov hydrochlorinations as reported by Nicewicz.
Figure 9: Mechanism for anti-Markovnikov hydrochlorination according to Ritter.
Scheme 29: anti-Markovnikov hydrochlorinations as reported by Nicewicz; rr (regioisomeric ratio) corresponds t...
Scheme 30: anti-Markovnikov hydrochlorinations as reported by Liu.
Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64
Graphical Abstract
Scheme 1: Overview of homopropargylic azides importance and strategies for azido-alkynylation.
Scheme 2: Screening of nucleophilic alkynes and investigation of the photocatalyst solubility. n.o = not obse...
Scheme 3: Selected scope entries of the azido-alkynylation. The data were already published in ref. [45].
Scheme 4: Unsuccessful examples. The conditions used are the same as in Scheme 3. The yields reported were determined...
Scheme 5: Proposed mechanism.
Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59
Graphical Abstract
Scheme 1: Background (a and b) and proposed carboamination MCR with diazo esters (c). a) Selected bioactive γ...
Scheme 2: Substrate scope of diazo compounds, 1,3-dienes and amines. aReactions (1/2/3/Pd(OAc)2/Xantphos = 0....
Scheme 3: Substrate scope of diazo compounds, allenes and amines. aReactions (1/5/3/Pd(OAc)2/Xantphos = 0.3.0...
Scheme 4: Mechanistic experiments. a) Radical trapping experiments with TEMPO. b) Exclusion of possible inter...
Scheme 5: Proposed mechanisms for the carboamination of 1,3-dienes or allenes with diazo esters and amines.
Scheme 6: Scale-up reactions and synthetic transformations. Reaction conditions: a) LiAlH4, THF, 0 °C; b) MeM...
Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35
Graphical Abstract
Scheme 1: Comparison between Barton and NHPI ester radical precursors.
Scheme 2: Overview of the mechanisms and activation modes involved in radical generation from RAEs.
Scheme 3: Common mechanisms in photocatalysis.
Scheme 4: A) Giese-type radical addition of NHPI esters mediated by a reductive quenching photocatalytic cycl...
Scheme 5: A) Minisci-type radical addition of NHPI esters. B) Reaction mechanism involving an “off-cycle” red...
Scheme 6: Activation of NHPI esters through hydrogen-bonding in an oxidative quenching photocatalytic cycle.
Scheme 7: SET activation of RAE facilitated by a Lewis acid catalyst.
Scheme 8: PCET activation of NHPI esters in the context of a radical-redox annulation.
Scheme 9: Activation enabled by a strong excited-state reductant catalyst and its application in the dearomat...
Scheme 10: Proposed formation of an intramolecular charge-transfer complex in the synthesis of (spiro)anellate...
Scheme 11: Formation of a charge-transfer complex between enamides and NHPI esters enabled by a chiral phospha...
Scheme 12: Activation of NHPI ester through the formation of photoactive EDA-complexes.
Scheme 13: A) EDA complex-mediated radical hydroalkylation reactions of NHPI esters. B) Proposed mechanism for...
Scheme 14: Proposed radical chain mechanism initiated by EDA-complex formation.
Scheme 15: A) Photoinduced decarboxylative borylation. B) Proposed radical chain mechanism.
Scheme 16: A) Activation of NHPI esters mediated by PPh3/NaI. B) Proposed catalytic cycle involving EDA-comple...
Scheme 17: A) Radical generation facilitated by EDA complex formation between PTH1 catalyst and NHPI esters. B...
Scheme 18: Proposed catalytic cycle for the difunctionalization of styrenes.
Scheme 19: Formation of a charge-transfer complex between NHPI esters and Cs2CO3 enables decarboxylative amina...
Scheme 20: 3-Acetoxyquinuclidine as catalytic donor in the activation of TCNHPI esters.
Scheme 21: A) Photoinduced Cu-catalyzed decarboxylative amination. B) Proposed catalytic cycle. C) Radical clo...
Scheme 22: A) Photoinduced Pd-catalyzed aminoalkylation of 1,4-dienes. B) Proposed catalytic cycle.
Scheme 23: A) TM-catalyzed decarboxylative coupling of NHPI esters and organometallic reagents. B) Representat...
Scheme 24: Synthetic applications of the TM-catalyzed decarboxylative coupling of NHPI esters and organometall...
Scheme 25: A) Ni-catalyzed cross-electrophile coupling of NHPI esters. B) Representative catalytic cycle.
Scheme 26: A) Synthetic applications of decarboxylative cross-electrophile couplings. B) Decarboxylative aryla...
Scheme 27: A) Activation of tetrachlorophthalimide redox-active esters enabled by a low-valency Bi complex. B)...
Scheme 28: Activation of NHPI esters mediated by Zn0 applied in a Z-selective alkenylation reaction.
Scheme 29: A) Activation of NHPI esters enabled by a pyridine-boryl radical species applied to the decarboxyla...
Scheme 30: A) Decarboxylative coupling of RAE and aldehydes enabled by NHC-catalyzed radical relay. B) Propose...
Scheme 31: A) Decarboxylative C(sp3)–heteroatom coupling reaction of NHPI esters under NHC catalysis B) The NH...
Scheme 32: A) Electrochemical Giese-type radical addition of NHPI esters. B) Reaction mechanism.
Scheme 33: Electrochemical Minisci-type radical addition of NHPI-esters.
Scheme 34: Ni-electrocatalytic cross-electrophile coupling of NHPI esters with aryl iodides.
Scheme 35: A) Decarboxylative arylation of NHPI esters under Ag-Ni electrocatalysis B) Formation of AgNP on th...
Scheme 36: Synthetic applications of decarboxylative couplings of NHPI esters under Ni-electrocatalysis.
Scheme 37: Examples of natural product syntheses in which RAEs were used in key C–C bond forming reactions.
Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131
Graphical Abstract
Scheme 1: Photocatalytic decarboxylative transformations mediated by the NaI/PPh3 catalyst system.
Scheme 2: Proposed catalytic cycle of NaI/PPh3 photoredox catalysis.
Scheme 3: Decarboxylative alkenylation of redox-active esters by NaI/PPh3 catalysis.
Scheme 4: Decarboxylative alkenylation mediated by NaI/PPh3 catalysis.
Scheme 5: NaI-mediated photoinduced α-alkenylation of Katritzky salts 7.
Scheme 6: n-Bu4NI-mediated photoinduced decarboxylative olefination.
Scheme 7: Proposed mechanism of the n-Bu4NI-mediated photoinduced decarboxylative olefination.
Scheme 8: Photodecarboxylative alkylation of redox-active esters with diazirines.
Scheme 9: Photoinduced iodine-anion-catalyzed decarboxylative/deaminative C–H alkylation of enamides.
Scheme 10: Photocatalytic C–H alkylation of coumarins mediated by NaI/PPh3 catalysis.
Scheme 11: Photoredox alkylation of aldimines by NaI/PPh3 catalysis.
Scheme 12: Photoredox C–H alkylation employing ammonium iodide.
Scheme 13: NaI/PPh3/CuBr cooperative catalysis for photocatalytic C(sp3)–O/N cross-coupling reactions.
Scheme 14: Proposed mechanism of NaI/PPh3/CuBr cooperative catalysis for photocatalytic C(sp3)–O/N cross-coupl...
Scheme 15: Photocatalytic decarboxylative [3 + 2]/[4 + 2] annulation between enynals and γ,σ-unsaturated N-(ac...
Scheme 16: Proposed mechanism for the decarboxylative [3 + 2]/[4 + 2] annulation.
Scheme 17: Decarboxylative cascade annulation of alkenes/1,6-enynes with N-hydroxyphthalimide esters.
Scheme 18: Decarboxylative radical cascade cyclization of N-arylacrylamides.
Scheme 19: NaI/PPh3-driven photocatalytic decarboxylative radical cascade alkylarylation.
Scheme 20: Proposed mechanism of the NaI/PPh3-driven photocatalytic decarboxylative radical cascade cyclizatio...
Scheme 21: Visible-light-promoted decarboxylative cyclization of vinylcycloalkanes.
Scheme 22: NaI/PPh3-mediated photochemical reduction and amination of nitroarenes.
Scheme 23: PPh3-catalyzed alkylative iododecarboxylation with LiI.
Scheme 24: Visible-light-triggered iodination facilitated by N-heterocyclic carbenes.
Scheme 25: Visible-light-induced photolysis of phosphonium iodide salts for monofluoromethylation.
Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116
Graphical Abstract
Scheme 1: Oxidation of catechol and subsequent cross-linking. Scheme 1 redrawn from [3].
Scheme 2: (A) Structure of typical urushiol in Chinese lacquer, and (B) schematic process of laccase-catalyze...
Scheme 3: A) Primary amino acid sequence of mfp-1, mfp-3, and mfp-5 (Y: DOPA, K: lysine). B) Scheme showing e...
Scheme 4: Activation–deactivation equilibrium in nitroxide-mediated polymerizations. Bicomponent initiating s...
Scheme 5: Mechanism of a transition metal complex-mediated ATRP. Scheme 5 redrawn from [14].
Scheme 6: Mechanism of RAFT polymerization. Scheme 6 redrawn from [68].
Scheme 7: Degenerative transfer (a) and reversible termination (b) mechanism of OMRP. Scheme 7 redrawn from [70].
Scheme 8: Simplified mechanism of a RITP. Scheme 8 redrawn from [21].
Scheme 9: (A) Structures of π-conjugated conductive polymers. (B) Examples of conductive polymer synthesis vi...
Scheme 10: Possible regiochemical couplings in PATs. Scheme 10 redrawn from [79].
Scheme 11: General thiol-ene photopolymerization process. Scheme 11 redrawn from [81].
Scheme 12: (a) Three generations of Grubbs catalysts. (b) Proposed mechanism for photo-ROMP via a reductive qu...
Scheme 13: Pyrylium and thiopyrylium salts studied by Boydston et al. Scheme 13 redrawn from [91].
Scheme 14: A general illustration of post-polymerization modification by thiol–ene chemistry.
Scheme 15: Introduction of functionalities by nitroxide radical coupling of HO-TEMPO derivatives.
Scheme 16: Chemical reaction process scheme of DCP-induced crosslinking of LDPE. Scheme 16 redrawn from [126].
Scheme 17: A probable mechanism of radical-induced hydrosilylation.
Scheme 18: Polymer surface modification by homolytic dediazonation of diazonium salts.
Scheme 19: Photoinduced polymer surface modification or surface grafting using benzophenone.
Scheme 20: Depolymerization mechanism of common photoresists. (a) A possible mechanism of radiation decomposit...
Scheme 21: Proposed mechanisms of photooxidative depolymerization of polystyrene. (a) Scheme 21a was reprinted with perm...
Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103
Graphical Abstract
Scheme 1: Air-promoted radical chain reaction of dialkylzinc reagents with α,β-unsaturated carbonyl compounds....
Scheme 2: Enolate formation by zinc radical transfer (SH2 on dialkylzinc reagents).
Scheme 3: Preparation of α-(aminomethyl)acrylate 10.
Scheme 4: Reaction of α-(aminomethyl)acrylate 10 with Et2Zn in the presence of air.
Scheme 5: Chemical correlation to determine the configuration of the major diastereomer of (RS)-14b.
Scheme 6: Air-promoted tandem 1,4-addition–aldol condensation reactions of Et2Zn with α-(aminomethyl)acrylate...
Scheme 7: Diagnostic experiments for a radical mechanism and for enolate formation.
Scheme 8: Diagnostic experiments with N-benzyl enoate 10.
Scheme 9: Reactivity manifolds for the air-promoted tandem 1,4-addition–electrophilic substitution reaction b...