Search for "elimination" in Full Text gives 836 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45
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.
Beilstein J. Org. Chem. 2025, 21, 407–411, doi:10.3762/bjoc.21.28
Graphical Abstract
Figure 1: The structures of veliparib and iVeliparib-AP6.
Scheme 1: The synthetic route for iVeliparib-AP6.
Figure 2: Identification of the cryptic impurity of iVeliparib. The UV trace of the initially purified iVelip...
Figure 3: The structures of 6 and 7 and the MS ion extraction traces of 3, 4, 6, and 7 from HPLC analysis of ...
Scheme 2: The conversion of byproduct 6 to 10 to facilitate its removal.
Figure 4: The LUMO and electrostatic charges of thalidomide and its derivatives by DFT calculation at the ωB9...
Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27
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].
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, 286–295, doi:10.3762/bjoc.21.21
Graphical Abstract
Scheme 1: Reaction of arylamines and MBH carbonates of isatins. Reaction conditions: MBH carbonate of isatin ...
Scheme 2: Reaction of arylamines and MBH maleimides of isatins. Reaction conditions: MBH maleimide of isatin ...
Figure 1: Single crystal structure of compound 5a.
Figure 2: Single crystal structure of compound 5j.
Scheme 3: Reactions of MBH carbonates of isatins and triphenylphosphine. Reaction conditions: MBH carbonate o...
Figure 3: Single crystal structure of compound 6e.
Figure 4: Single crystal structure of compound 7a.
Figure 5: Single crystal structure of compound 8a.
Scheme 4: Proposed reaction mechanism for the various compounds.
Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12
Graphical Abstract
Scheme 1: Formation of isocyanates and amidated arenes from dioxazolones.
Scheme 2: Copper-catalyzed synthesis of δ-lactams via open-shell copper nitrenoid transfer. aCuBr (10 mol %) ...
Figure 1: Proposed reaction pathway for the copper-catalyzed synthesis of δ-lactams from dioxazolones.
Scheme 3: Copper(II)-catalyzed synthesis of 1,2,4-triazole derivatives.
Figure 2: Proposed reaction mechanism for the copper-catalyzed synthesis of 1,2,4-triazole analogues from dio...
Scheme 4: Copper(I)-catalyzed synthesis of N-acyl amidines from dioxazolones, acetylenes, and amines. aPerfor...
Figure 3: Proposed reaction mechanism for the copper(I)-catalyzed synthesis of N-acyl amidines.
Scheme 5: Preparation of N-arylamides from dioxazolones and boronic acids using a copper salt.
Figure 4: Proposed reaction pathway for the copper-mediated synthesis of N-arylamides from dioxazolones.
Scheme 6: Copper-catalyzed preparation of N-acyl iminophosphoranes from dioxazolones.
Figure 5: Proposed reaction pathway for the copper-catalyzed synthesis of N-acyl iminophosphoranes from dioxa...
Scheme 7: Copper-catalyzed synthesis of N-acyl sulfenamides. a1.0 equiv of 18 and 2.0 equiv of 19 were used. b...
Figure 6: Proposed reaction mechanism for the copper-catalyzed S-amidation of thiols.
Scheme 8: Copper-catalyzed asymmetric hydroamidation of vinylarenes. a4 mol % + 2 mol % catalyst was used. b4...
Figure 7: Proposed reaction mechanism for the copper-catalyzed hydroamidation of vinylarenes.
Scheme 9: Copper-catalyzed anti-Markovnikov hydroamidation of alkynes.
Figure 8: Proposed reaction mechanism for the copper-catalyzed amidation of alkynes.
Scheme 10: Copper-catalyzed preparation of primary amides through N–O bond reduction using reducing agent.
Figure 9: Proposed catalytic cycle for the copper-catalyzed reduction of dioxazolones.
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. 2025, 21, 146–154, doi:10.3762/bjoc.21.8
Graphical Abstract
Scheme 1: C–F bond activation through β-fluorine elimination via metalacyclopropanes.
Scheme 2: Synthesis of 2-arylbenzofurans 3 via the coupling of 1 with 2. Isolated yields are given. aNi(cod)2...
Scheme 3: Synthesis of 2-phenylbenzothiophene (5).
Scheme 4: Orthogonal approach to 2,5-diarylbenzofuran 3fa.
Scheme 5: Possible mechanisms.
Scheme 6: Formation of nickelacyclopropane Eb in a stoichiometric reaction.
Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7
Graphical Abstract
Figure 1: Plausible general catalytic activation for ionic or radical mechanisms.
Scheme 1: Synthesis of α-aminonitriles 1.
Scheme 2: Synthesis of β-amino ketone or β-amino ester derivatives 3.
Scheme 3: Synthesis of 1-(α-aminoalkyl)-2-naphthol derivatives 4.
Scheme 4: Synthesis of thioaminals 5.
Scheme 5: Synthesis of aryl- or amine-containing alkanes 6 and 7.
Scheme 6: Synthesis of 1-aryl-2-sulfonamidopropanes 8.
Scheme 7: Synthesis of α-substituted propargylamines 10.
Scheme 8: Synthesis of N-propargylcarbamates 11.
Scheme 9: Synthesis of (E)-vinyl sulfones 12.
Scheme 10: Synthesis of o-halo-substituted aryl chalcogenides 13.
Scheme 11: Synthesis of α-aminophosphonates 14.
Scheme 12: Synthesis of unsaturated furanones and pyranones 15–17.
Scheme 13: Synthesis of substituted dihydropyrimidines 18.
Scheme 14: Regioselective synthesis of 1,4-dihydropyridines 20.
Scheme 15: Synthesis of tetrahydropyridines 21.
Scheme 16: Synthesis of furoquinoxalines 22.
Scheme 17: Synthesis of 2,4-substituted quinolines 23.
Scheme 18: Synthesis of cyclic ether-fused tetrahydroquinolines 24.
Scheme 19: Practical route for 1,2-dihydroisoquinolines 25.
Scheme 20: Synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives 26.
Scheme 21: Synthesis of polysubstituted pyrroles 27.
Scheme 22: Enantioselective synthesis of polysubstituted pyrrolidines 30 directed by the copper complex 29.
Scheme 23: Synthesis of 4,5-dihydropyrazoles 31.
Scheme 24: Synthesis of 2 arylisoindolinones 32.
Scheme 25: Synthesis of imidazo[1,2-a]pyridines 33.
Scheme 26: Synthesis of isoxazole-linked imidazo[1,2-a]azines 35.
Scheme 27: Synthesis of 2,3-dihydro-1,2,4-triazoles 36.
Scheme 28: Synthesis of naphthopyrans 37.
Scheme 29: Synthesis of benzo[g]chromene derivatives 38.
Scheme 30: Synthesis of naphthalene annulated 2-aminothiazoles 39, piperazinyl-thiazoloquinolines 40 and thiaz...
Scheme 31: Synthesis of furo[3,4-b]pyrazolo[4,3-f]quinolinones 42.
Scheme 32: Synthesis of spiroindoline-3,4’-pyrano[3,2-b]pyran-4-ones 43.
Scheme 33: Synthesis of N-(α-alkoxy)alkyl-1,2,3-triazoles 44.
Scheme 34: Synthesis of 4-(α-tetrasubstituted)alkyl-1,2,3-triazoles 45.
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.
Beilstein J. Org. Chem. 2025, 21, 1–7, doi:10.3762/bjoc.21.1
Graphical Abstract
Figure 1: Structures of compounds 1–3 and the polycyclic skeleton of 1 as mapped on a carbon schwarzite unit ...
Scheme 1: a) Synthesis of 1; b) reactions of 1; c) synthesis of 3.
Figure 2: (a) Structures of 1 in the colorless crystal; (b) structures of (P,M,P)-1 in the yellow crystal. (C...
Figure 3: Structure of (M,P,M)-3 in the crystal of 3·CH2Cl2 (carbon and oxygen atoms are shown as grey and re...
Figure 4: UV–vis absorption spectrum (black line) and emission spectrum (blue line, excited at 400 nm) of com...
Beilstein J. Org. Chem. 2024, 20, 3215–3220, doi:10.3762/bjoc.20.267
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.
Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263
Graphical Abstract
Figure 1: Representative examples of fluorine containing, biologically active compounds.
Scheme 1: Strategies for the synthesis of α-alkyl sulfoxonium ylides.
Scheme 2: Exploring substrate scope in the direct α-fluoroalkylation of sulfoxonium ylides.
Scheme 3: Synthetic applications of fluoroalkylated sulfoxonium ylides.
Figure 2: Possible mechanisms for the reaction of 1a and 2a leading to 3a (via B), proceeding via either halo...
Figure 3: Electrostatic potential of 2a’ from 0.075 e to 0.21 e, showing two sigma holes of potentials 0.20 a...
Figure 4: The optimized reaction coordinate diagrams for the halogen bond-mediated mechanism (path 1, left) a...
Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258
Graphical Abstract
Figure 1: Example bioactive compounds containing cyclic scaffolds potentially accessible by HVI chemistry.
Figure 2: A general mechanism for HVI-mediated endo- or exo-halocyclisation.
Scheme 1: Metal-free synthesis of β-fluorinated piperidines 6. Ts = tosyl.
Scheme 2: Intramolecular aminofluorination of unactivated alkenes with a palladium catalyst.
Scheme 3: Aminofluorination of alkenes in the synthesis of enantiomerically pure β-fluorinated piperidines. P...
Scheme 4: Synthesis of β-fluorinated piperidines.
Scheme 5: Intramolecular fluoroaminations of unsaturated amines published by Li.
Scheme 6: Intramolecular aminofluorination of unsaturated amines using 1-fluoro-3,3-dimethylbenziodoxole (12)...
Scheme 7: 3-fluoropyrrolidine synthesis. aDiastereomeric ratio (cis/trans) determined by 19F NMR analysis.
Scheme 8: Kitamura’s synthesis of 3-fluoropyrrolidines. Values in parentheses represent the cis:trans ratio.
Scheme 9: Jacobsen’s enantio- and diastereoselective protocol for the synthesis of syn-β-fluoroaziridines 15.
Scheme 10: Different HVI reagents lead to different diastereoselectivity in aminofluorination competing with c...
Scheme 11: Fluorocyclisation of unsaturated alcohols and carboxylic acids to make tetrahydrofurans, fluorometh...
Scheme 12: Oxyfluorination of unsaturated alcohols.
Scheme 13: Synthesis and mechanism of fluoro-benzoxazepines.
Scheme 14: Intramolecular fluorocyclisation of unsaturated carboxylic acids. Yield of isolated product within ...
Scheme 15: Synthesis of fluorinated tetrahydrofurans and butyrolactone.
Scheme 16: Synthesis of fluorinated oxazolines 32. aReaction time increased to 40 hours. Yields refer to isola...
Scheme 17: Electrochemical synthesis of fluorinated oxazolines.
Scheme 18: Electrochemical synthesis of chromanes.
Scheme 19: Synthesis of fluorinated oxazepanes.
Scheme 20: Enantioselective oxy-fluorination with a chiral aryliodide catayst.
Scheme 21: Catalytic synthesis of 5‑fluoro-2-aryloxazolines using BF3·Et2O as a source of fluoride and an acti...
Scheme 22: Intramolecular carbofluorination of alkenes.
Scheme 23: Intramolecular chlorocyclisation of unsaturated amines.
Scheme 24: Synthesis of chlorinated cyclic guanidines 44.
Scheme 25: Synthesis of chlorinated pyrido[2,3-b]indoles 46.
Scheme 26: Chlorolactonization and chloroetherification reactions.
Scheme 27: Proposed mechanism for the synthesis of chloromethyl oxazolines 49.
Scheme 28: Oxychlorination to form oxazine and oxazoline heterocycles promoted by BCl3.
Scheme 29: Aminobromocyclisation of homoallylic sulfonamides 53. The cis:trans ratios based on the 1H NMR of t...
Scheme 30: Synthesis of cyclic imines 45.
Scheme 31: Synthesis of brominated pyrrolo[2,3-b]indoles 59.
Scheme 32: Bromoamidation of alkenes.
Scheme 33: Synthesis of brominated cyclic guanidines 61 and 61’.
Scheme 34: Intramolecular bromocyclisation of N-oxyureas.
Scheme 35: The formation of 3-bromoindoles.
Scheme 36: Bromolactonisation of unsaturated acids 68.
Scheme 37: Synthesis of 5-bromomethyl-2-oxazolines.
Scheme 38: Synthesis of brominated chiral morpholines.
Scheme 39: Bromoenolcyclisation of unsaturated dicarbonyl groups.
Scheme 40: Brominated oxazines and oxazolines with BBr3.
Scheme 41: Synthesis of 5-bromomethtyl-2-phenylthiazoline.
Scheme 42: Intramolecular iodoamination of unsaturated amines.
Scheme 43: Formation of 3-iodoindoles.
Scheme 44: Iodoetherification of 2,2-diphenyl-4-penten-1-carboxylic acid (47’) and 2,2-diphenyl-4-penten-1-ol (...
Scheme 45: Synthesis of 5-iodomethyl-2-oxazolines.
Scheme 46: Synthesis of chiral iodinated morpholines. aFrom the ʟ-form of the amino acid starting material. Th...
Scheme 47: Iodoenolcyclisation of unsaturated dicarbonyl compounds 74.
Scheme 48: Synthesis of 5-iodomethtyl-2-phenylthiazoline (87).
Beilstein J. Org. Chem. 2024, 20, 3077–3084, doi:10.3762/bjoc.20.256
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...
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, 2946–2953, doi:10.3762/bjoc.20.247
Graphical Abstract
Scheme 1: Generation of gem-difluorovinyl and trifluorovinyl Michael acceptors and their use in the synthesis...
Scheme 2: Formation of α,β-difluorinated and α-fluorinated α,β-unsaturated amides.
Scheme 3: Formation of β-fluorinated and nonfluorinated α,β-unsaturated amides.
Scheme 4: Michael addition of 1a–d with tert-BuLi.
Scheme 5: Michael addition of 2a–d with tert-BuLi.
Scheme 6: Formation of N-methylation products.
Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243
Graphical Abstract
Figure 1: Various structures of iodonium salts.
Scheme 1: Αrylation of α-fluoroacetoacetamides 5 to α-aryl-α-fluoroacetoacetamides 7 and α-fluoroacetamides 8...
Scheme 2: Proposed mechanism for the arylation of α-fluoroacetoacetamides 5 to α-aryl-α-fluoroacetoacetamides ...
Scheme 3: α-Arylation of α-nitro- and α-cyano derivatives of α-fluoroacetamides 9 employing unsymmetrical DAI...
Scheme 4: Synthesis of α,α-difluoroketones 13 by reacting α,α-difluoro-β-keto acid esters 11 with aryl(TMP)io...
Scheme 5: Coupling reaction of arynes generated by iodonium salts 6 and arynophiles 14 for the synthesis of t...
Scheme 6: Metal-free arylation of quinoxalines 17 and quinoxalinones 19 with DAISs 16.
Scheme 7: Transition-metal-free, C–C cross-coupling of 2-naphthols 21 to 1-arylnapthalen-2-ols 22 employing d...
Scheme 8: Arylation of vinyl pinacol boronates 23 to trans-arylvinylboronates 24 in presence of hypervalent i...
Scheme 9: Light-induced selective arylation at C2 of quinoline N-oxides 25 and pyridine N-oxides 28 in the pr...
Scheme 10: Plaussible mechanism for the light-induced selective arylation of N-heterobiaryls.
Scheme 11: Photoinduced arylation of heterocycles 31 with the help of diaryliodonium salts 16 activated throug...
Scheme 12: Arylation of MBH acetates 33 with DIPEA and DAIRs 16.
Scheme 13: Aryl sulfonylation of MBH acetates 33 with DABSO and diphenyliodonium triflates 16.
Scheme 14: Synthesis of oxindoles 37 from N-arylacrylamides 36 and diaryliodonium salts 26.
Scheme 15: Mechanically induced N-arylation of amines 38 using diaryliodonium salts 16.
Scheme 16: o-Fluorinated diaryliodonium salts 40-mediated diarylation of amines 38.
Scheme 17: Proposed mechanism for the diarylation of amines 38 using o-fluorinated diaryliodonium salts 40.
Scheme 18: Ring-opening difunctionalization of aliphatic cyclic amines 41.
Scheme 19: N-Arylation of amino acid esters 44 using hypervalent iodonium salts 45.
Scheme 20: Regioselective N-arylation of triazole derivatives 47 by hypervalent iodonium salts 48.
Scheme 21: Regioselective N-arylation of tetrazole derivatives 50 by hypervalent iodonium salt 51.
Scheme 22: Selective arylation at nitrogen and oxygen of pyridin-2-ones 53 by iodonium salts 16 depending on t...
Scheme 23: N-Arylation using oxygen-bridged acyclic diaryliodonium salt 56.
Scheme 24: The successive C(sp2)–C(sp2)/O–C(sp2) bond formation of naphthols 58.
Scheme 25: Synthesis of diarylethers 62 via in situ generation of hypervalent iodine salts.
Scheme 26: O-Arylated galactosides 64 by reacting protected galactosides 63 with hypervalent iodine salts 16 i...
Scheme 27: Esterification of naproxen methyl ester 65 via formation and reaction of naproxen-containing diaryl...
Scheme 28: Etherification and esterification products 72 through gemfibrozil methyl ester-derived diaryliodoni...
Scheme 29: Synthesis of iodine containing meta-substituted biaryl ethers 74 by reacting phenols 61 and cyclic ...
Scheme 30: Plausible mechanism for the synthesis of meta-functionalized biaryl ethers 74.
Scheme 31: Intramolecular aryl migration of trifluoromethane sulfonate-substituted diaryliodonium salts 75.
Scheme 32: Synthesis of diaryl ethers 80 via site-selective aryl migration.
Scheme 33: Synthesis of O-arylated N-alkoxybenzamides 83 using aryl(trimethoxyphenyl)iodonium salts 82.
Scheme 34: Synthesis of aryl sulfides 85 from thiols 84 using diaryliodonium salts 16 in basic conditions.
Scheme 35: Base-promoted synthesis of diarylsulfoxides 87 via arylation of general sulfinates 86.
Scheme 36: Plausible mechanism for the arylation of sulfinates 86 via sulfenates A to give diaryl sulfoxides 87...
Scheme 37: S-Arylation reactions of aryl or heterocyclic thiols 88.
Scheme 38: Site-selective S-arylation reactions of cysteine thiol groups in 91 and 94 in the presence of diary...
Scheme 39: The selective S-arylation of sulfenamides 97 using diphenyliodonium salts 98.
Scheme 40: Plausible mechanism for the synthesis of sulfilimines 99.
Scheme 41: Synthesis of S-arylxanthates 102 by reacting DAIS 101 with potassium alkyl xanthates 100.
Figure 2: Structured of the 8-membered and 4-membered heterotetramer I and II.
Scheme 42: S-Arylation by diaryliodonium cations 103 using KSCN (104) as a sulfur source.
Scheme 43: S-Arylation of phosphorothioate diesters 107 through the utilization of diaryliodonium salts 108.
Scheme 44: Transfer of the aryl group from the hypervalent iodonium salt 108 to phosphorothioate diester 107.
Scheme 45: Synthesis of diarylselenides 118 via diarylation of selenocyanate 115.
Scheme 46: Light-promoted arylation of tertiary phosphines 119 to quaternary phosphonium salts 121 using diary...
Scheme 47: Arylation of aminophosphorus substrate 122 to synthesize phosphine oxides 123 using aryl(mesityl)io...
Scheme 48: Reaction of diphenyliodonium triflate (16) with DMSO (124) via thia-Sommelet–Hauser rearrangement.
Scheme 49: Synthesis of biaryl compounds 132 by reacting diaryliodonium salts 131 with arylhydroxylamines 130 ...
Scheme 50: Synthesis of substituted indazoles 134 and 135 from N-hydroxyindazoles 133.
Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240
Graphical Abstract
Scheme 1: Structures of indigo (1a), indirubin (2a) and isoindigo (3a).
Scheme 2: Structures of akashins A–C.
Scheme 3: Synthesis of 5b. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −20 °C, 1.5 h, then 20 °C, 8–1...
Scheme 4: Synthesis of 7c. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −18 °C, 3 h; then: TMSOTf, 4 Å...
Scheme 5: Synthesis of 1d. Reagents and conditions: i) chloroacetic acid, Na2CO3, reflux, 6 h; ii) Ac2O, NaOA...
Scheme 6: Synthesis of 10e. Reagents and conditions: i) p-TsOH·H2O, acetonitrile, MeOH, 1 d; ii) NIS, PPh3, D...
Scheme 7: Synthesis of akashins A–C. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −18 to 20 °C, 15 h; ...
Scheme 8: Synthesis of 5d. Reagents and conditions: i) KMnO4, AcOH, high-power-stirring (12.000 rot/min), 20 ...
Scheme 9: Possible mechanism of the formation of 5c.
Scheme 10: Synthesis of 7d. Reagents and conditions: i) 1) CH2Cl2, 2) Me3SiI, 20 °C, 30 min, 3) 0 °C, 30 min, ...
Scheme 11: Synthesis of α-15b. Reagents and conditions: i) 1) CH2Cl2, 2) Me3SiI, 20 °C, 30 min, 3) 0 °C, 30 mi...
Scheme 12: Synthesis of isatin-N-glycosides 16a–f. Reagents and conditions: i) PhNH2, EtOH, 20 °C, 12 h; ii) Ac...
Scheme 13: Synthesis of 17–21. Reagents and conditions: i) Na2CO3, MeOH, 20 °C, 4 h.
Scheme 14: Synthesis of indirubin-N-glycosides α-17a and α-17b.
Scheme 15: Synthesis of β-17f. Reagents and conditions: i) 1) Na2CO3, MeOH, 20 °C, 4 h, 2) Ac2O/pyridine 1:1, ...
Scheme 16: Synthesis of β-24a. Reagents and conditions: i) n-PrOH, H2O, formic acid (buffer, 100 mM), 2 h, 65 ...
Scheme 17: Synthesis of isatin-N-glycosides 23b–g and 24b–g.
Scheme 18: Synthesis of β-29a,b. Reagents and conditions: i) EtOH, 20 °C, 12 h; ii) DDQ, dioxane, 20 °C, 12 h;...
Scheme 19: Synthesis of β-31a. Reagents and conditions: i) Na2SO3, dioxane, H2O, 110 °C, 2 d; ii) piperidine, ...
Scheme 20: Synthesis of 33a–d. Reagents and conditions: i) Ac2O, AcOH, NaOAc, 80 °C, 1 h; ii) 1) NaOMe, anhydr...
Scheme 21: Indirubins 34 and 35.
Scheme 22: Synthesis of 36f. Reagents and conditions: i) NaOH, H2O, 20 °C, 5 h; ii) HCl, NaNO2, H2O, −14 °C; i...
Scheme 23: Synthesis of 38a–h. Reagents and conditions: i) 1) 0.1 equiv NaOMe, MeOH, 20 °C, 15–20 min, 2) HOAc...
Scheme 24: Synthesis of 40a–h. Reagents and conditions: i) method A: EtOH/THF, cat. KOt-Bu, 20 °C, 3–4.5 h; me...
Scheme 25: Synthesis of 41a–d. Reagents and conditions: i) Ac2O, AcOH, NaOAc, 80 °C, 1 h.
Scheme 26: Synthesis of 41e. Reagents and conditions: i) AcOH, NaOAc, 110 °C, 24 h.
Scheme 27: Synthesis of E-β-43a–e and E-β-44a,b. Reagents and conditions: i) 1) NEt3, EtOH, 20 °C, 12 h, 2) DM...
Scheme 28: Synthesis of E-43f. Reagents and conditions: i) Na2CO3, MeOH, 20 °C, 6–24 h.
Scheme 29: Synthesis of 46a–m. Reagents and conditions: i) NEt3 (1 equiv), EtOH, 20 °C, 6–10 h; ii) MsCl, NEt3...
Scheme 30: Synthesis of 48a–d. Reagents and conditions: i) AcOH/Ac2O, NaOAc, 60 °C, 3–4 h.
Scheme 31: Synthesis of 48e. Reagents and conditions: i) NaOAc, AcOH, 110 °C, 24 h.
Scheme 32: Synthesis of β-49a,b. Reagents and conditions: i) AcOH/Ac2O, NaOAc, 60 °C, 3–4 h.
Scheme 33: Synthesis of β-54a,b. Reagents and conditions: i) 1) NaH, DMF, 0 °C, 15 min, 2) β-51a,b, 20 °C, 3 h...
Scheme 34: Synthesis of 54c–l. The yields refer to the yields of the first and second condensation step for ea...
Scheme 35: Synthesis of 57a–c and 58a–d. Reagents and conditions: i) HCl (conc.), AcOH, reflux, 24 h; ii) 1) B...
Scheme 36: Synthesis of 59a–e and 60a–e. Reagents and conditions: i) P(NEt2)3 (1.1 equiv), CH2Cl2, −78 °C to 2...
Scheme 37: Synthesis of 61a–d and 62a–d. Reagents and conditions: i) P(NEt2)3 (1.1 equiv), CH2Cl2, −78 °C to 2...
Scheme 38: Synthesis of β-64a–e and α-64a. Reagents and conditions: i) AcOH, Ac2O, NaOAc, 90 °C, 6 h.
Scheme 39: Synthesis of β-72a. Reagents and conditions: i) 66, EtOH, 20 °C, 12 h; ii) DDQ, dioxane, 20 °C, 12 ...
Scheme 40: Synthesis of β-72b.
Scheme 41: Synthesis of β-74a–c. Reagents and conditions: i) AcOH, Ac2O, NaOAc, 130 °C, 2 d.
Scheme 42: Synthesis of β-77. Reagents and conditions: i) 1) NEt3, EtOH, 20 °C, 12 h, 2) DMAP, NEt3, MsCl, 0 °...
Scheme 43: Synthesis of β-81a–f and β-80g. Reagents and conditions: i) AcOH, 80 °C, 1–3 h; ii) benzene, PTSA, ...
Scheme 44: Synthesis of 84a. Reagents and conditions: i) benzene, AlCl3, 20 °C, 10 min; ii) MeOH, NaOMe, 12 h,...
Scheme 45: Synthesis of 84b–l. The yields refer to the yields of the condensation and the deprotection step fo...
Beilstein J. Org. Chem. 2024, 20, 2827–2833, doi:10.3762/bjoc.20.238
Graphical Abstract
Scheme 1: Synthesis of polyfunctionalized methane derivatives through successive nucleophilic additions to th...
Scheme 2: Cyclization of 4a quenched by D2O.
Scheme 3: Plausible mechanisms for the ring closure of 4.
Scheme 4: Hydration of the ethynyl group of 4a.
Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233
Graphical Abstract
Figure 1: Various applications of tetrafluoroethylenated molecules.
Scheme 1: Precedent synthetic approaches to optically active compounds possessing a tetrafluoroethylene group...
Scheme 2: Synthetic strategy for preparing fluorine-containing amines via [1,3]-proton shift reactions.
Scheme 3: Preparation of the substrates used in this study.
Scheme 4: Derivatization of (S)-20b to (S)-23b for determining the optical purity of (S)-20b.
Scheme 5: Substrate scope for the present [1,3]-proton shift reaction. aYields are determined by 19F NMR spec...
Scheme 6: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2024, 20, 2691–2703, doi:10.3762/bjoc.20.226
Graphical Abstract
Scheme 1: Synthesis of monofluoroalkenes using fluorine-containing building blocks.
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, 2493–2499, doi:10.3762/bjoc.20.213
Graphical Abstract
Scheme 1: Strategies for Achmatowicz rearrangement.
Figure 1: Scope of the integrated continuous photo-flow (visible light)-induced Achmatowicz rearrangement rea...
Figure 2: Proposed mechanism for the photochemically induced Achmatowicz rearrangement.
Beilstein J. Org. Chem. 2024, 20, 2434–2441, doi:10.3762/bjoc.20.207
Graphical Abstract
Figure 1: Examples of trifluoromethoxylated drugs.
Scheme 1: Proposed mechanism of the reaction and 19F NMR of the DDPYOCF3/PhSeBr mixture.
Scheme 2: Phenylseleno trifluoromethoxylation of various alkenes. Yields determined by 19F NMR spectroscopy w...
Scheme 3: Degradation of 2a under acidic conditions.
Scheme 4: Radical deselenylation of 2. Yields determined by 19F NMR spectroscopy with PhCF3 as internal stand...