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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, 504–539, doi:10.3762/bjoc.20.45
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Beilstein J. Org. Chem. 2022, 18, 788–795, doi:10.3762/bjoc.18.79
Graphical Abstract
Scheme 1: Envisioned Minisci perfluoroalkylation facilitated by “dummy group” reagents 1a–c.
Scheme 2: Control experiments for the nucleophilic substitution of perfluoroalkylsulfinates 2 and halogenated...
Scheme 3: Left: isolated yields of synthesized perfluoroalkylating reagents: perfluorobutyl (1a), perfluorohe...
Scheme 4: Radical trapping experiment with 1,1-diphenylethylene (7) and 1b confirming the initially proposed ...
Scheme 5: Demonstrative scope for the perfluoroalkylation of aromatics. Isolated yields are shown in parenthe...
Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126
Graphical Abstract
Scheme 1: Schematic overview of transition metals studied in C–H activation processes.
Scheme 2: (A) Known biological activities related to benzimidazole-based compounds; (B and C) an example of a...
Scheme 3: (A) Known biological activities related to quinoline-based compounds; (B and C) an example of a sca...
Scheme 4: (A) Known biological activities related to sulfur-containing compounds; (B and C) an example of a s...
Scheme 5: (A) Known biological activities related to aminoindane derivatives; (B and C) an example of a scand...
Scheme 6: (A) Known biological activities related to norbornane derivatives; (B and C) an example of a scandi...
Scheme 7: (A) Known biological activities related to aniline derivatives; (B and C) an example of a titanium-...
Scheme 8: (A) Known biological activities related to cyclohexylamine derivatives; (B) an example of an intram...
Scheme 9: (A) Known biologically active benzophenone derivatives; (B and C) photocatalytic oxidation of benzy...
Scheme 10: (A) Known bioactive fluorine-containing compounds; (B and C) vanadium-mediated C(sp3)–H fluorinatio...
Scheme 11: (A) Known biologically active Lythraceae alkaloids; (B) synthesis of (±)-decinine (30).
Scheme 12: (A) Synthesis of (R)- and (S)-boehmeriasin (31); (B) synthesis of phenanthroindolizidines by vanadi...
Scheme 13: (A) Known bioactive BINOL derivatives; (B and C) vanadium-mediated oxidative coupling of 2-naphthol...
Scheme 14: (A) Known antiplasmodial imidazopyridazines; (B) practical synthesis of 41.
Scheme 15: (A) Gold-catalyzed drug-release mechanism using 2-alkynylbenzamides; (B and C) chromium-mediated al...
Scheme 16: (A) Examples of anti-inflammatory benzaldehyde derivatives; (B and C) chromium-mediated difunctiona...
Scheme 17: (A and B) Manganese-catalyzed chemoselective intramolecular C(sp3)–H amination; (C) late-stage modi...
Scheme 18: (A and B) Manganese-catalyzed C(sp3)–H amination; (C) late-stage modification of a leelamine deriva...
Scheme 19: (A) Known bioactive compounds containing substituted N-heterocycles; (B and C) manganese-catalyzed ...
Scheme 20: (A) Known indoles that present GPR40 full agonist activity; (B and C) manganese-catalyzed C–H alkyl...
Scheme 21: (A) Examples of known biaryl-containing drugs; (B and C) manganese-catalyzed C–H arylation through ...
Scheme 22: (A) Known zidovudine derivatives with potent anti-HIV properties; (B and C) manganese-catalyzed C–H...
Scheme 23: (A and B) Manganese-catalyzed C–H organic photo-electrosynthesis; (C) late-stage modification.
Scheme 24: (A) Example of a known antibacterial silylated dendrimer; (B and C) manganese-catalyzed C–H silylat...
Scheme 25: (A and B) Fe-based small molecule catalyst applied for selective aliphatic C–H oxidations; (C) late...
Scheme 26: (A) Examples of naturally occurring gracilioethers; (B) the first total synthesis of gracilioether ...
Scheme 27: (A and B) Selective aliphatic C–H oxidation of amino acids; (C) late-stage modification of proline-...
Scheme 28: (A) Examples of Illicium sesquiterpenes; (B) first chemical synthesis of (+)-pseudoanisatin (80) in...
Scheme 29: (A and B) Fe-catalyzed deuteration; (C) late-stage modification of pharmaceuticals.
Scheme 30: (A and B) Biomimetic Fe-catalyzed aerobic oxidation of methylarenes to benzaldehydes (PMHS, polymet...
Scheme 31: (A) Known tetrahydroquinolines with potential biological activities; (B and C) redox-selective Fe c...
Scheme 32: (A) Known drugs containing a benzofuran unit; (B and C) Fe/Cu-catalyzed tandem O-arylation to acces...
Scheme 33: (A) Known azaindolines that act as M4 muscarinic acetylcholine receptor agonists; (B and C) intramo...
Scheme 34: (A) Known indolinones with anticholinesterase activity; (B and C) oxidative C(sp3)–H cross coupling...
Scheme 35: (A and B) Cobalt-catalyzed C–H alkenylation of C-3-peptide-containing indoles; (C) derivatization b...
Scheme 36: (A) Cobalt-Cp*-catalyzed C–H methylation of known drugs; (B and C) scope of the o-methylated deriva...
Scheme 37: (A) Known lasalocid A analogues; (B and C) three-component cobalt-catalyzed C–H bond addition; (D) ...
Scheme 38: (A and B) Cobalt-catalyzed C(sp2)–H amidation of thiostrepton.
Scheme 39: (A) Known 4H-benzo[d][1,3]oxazin-4-one derivatives with hypolipidemic activity; (B and C) cobalt-ca...
Scheme 40: (A and B) Cobalt-catalyzed C–H arylation of pyrrole derivatives; (C) application for the synthesis ...
Scheme 41: (A) Known 2-phenoxypyridine derivatives with potent herbicidal activity; (B and C) cobalt-catalyzed...
Scheme 42: (A) Natural cinnamic acid derivatives; (B and C) cobalt-catalyzed C–H carboxylation of terminal alk...
Scheme 43: (A and B) Cobalt-catalyzed C–H borylation; (C) application to the synthesis of flurbiprofen.
Scheme 44: (A) Benzothiazoles known to present anticonvulsant activities; (B and C) cobalt/ruthenium-catalyzed...
Scheme 45: (A and B) Cobalt-catalyzed oxygenation of methylene groups towards ketone synthesis; (C) synthesis ...
Scheme 46: (A) Known anticancer tetralone derivatives; (B and C) cobalt-catalyzed C–H difluoroalkylation of ar...
Scheme 47: (A and B) Cobalt-catalyzed C–H thiolation; (C) application in the synthesis of quetiapine (153).
Scheme 48: (A) Known benzoxazole derivatives with anticancer, antifungal, and antibacterial activities; (B and...
Scheme 49: (A and B) Cobalt-catalyzed C–H carbonylation of naphthylamides; (C) BET inhibitors 158 and 159 tota...
Scheme 50: (A) Known bioactive pyrrolo[1,2-a]quinoxalin-4(5H)-one derivatives; (B and C) cobalt-catalyzed C–H ...
Scheme 51: (A) Known antibacterial cyclic sulfonamides; (B and C) cobalt-catalyzed C–H amination of propargyli...
Scheme 52: (A and B) Cobalt-catalyzed intramolecular 1,5-C(sp3)–H amination; (C) late-stage functionalization ...
Scheme 53: (A and B) Cobalt-catalyzed C–H/C–H cross-coupling between benzamides and oximes; (C) late-state syn...
Scheme 54: (A) Known anticancer natural isoquinoline derivatives; (B and C) cobalt-catalyzed C(sp2)–H annulati...
Scheme 55: (A) Enantioselective intramolecular nickel-catalyzed C–H activation; (B) bioactive obtained motifs;...
Scheme 56: (A and B) Nickel-catalyzed α-C(sp3)–H arylation of ketones; (C) application of the method using kno...
Scheme 57: (A and B) Nickel-catalyzed C(sp3)–H acylation of pyrrolidine derivatives; (C) exploring the use of ...
Scheme 58: (A) Nickel-catalyzed C(sp3)–H arylation of dioxolane; (B) library of products obtained from biologi...
Scheme 59: (A) Intramolecular enantioselective nickel-catalyzed C–H cycloalkylation; (B) product examples, inc...
Scheme 60: (A and B) Nickel-catalyzed C–H deoxy-arylation of azole derivatives; (C) late-stage functionalizati...
Scheme 61: (A and B) Nickel-catalyzed decarbonylative C–H arylation of azole derivatives; (C) application of t...
Scheme 62: (A and B) Another important example of nickel-catalyzed C–H arylation of azole derivatives; (C) app...
Scheme 63: (A and B) Another notable example of a nickel-catalyzed C–H arylation of azole derivatives; (C) lat...
Scheme 64: (A and B) Nickel-based metalorganic framework (MOF-74-Ni)-catalyzed C–H arylation of azole derivati...
Scheme 65: (A) Known commercially available benzothiophene-based drugs; (B and C) nickel-catalyzed C–H arylati...
Scheme 66: (A) Known natural tetrahydrofuran-containing substances; (B and C) nickel-catalyzed photoredox C(sp3...
Scheme 67: (A and B) Another notable example of a nickel-catalyzed photoredox C(sp3)–H alkylation/arylation; (...
Scheme 68: (A) Electrochemical/nickel-catalyzed C–H alkoxylation; (B) achieved scope, including three using na...
Scheme 69: (A) Enantioselective photoredox/nickel catalyzed C(sp3)–H arylation; (B) achieved scope, including ...
Scheme 70: (A) Known commercially available trifluoromethylated drugs; (B and C) nickel-catalyzed C–H trifluor...
Scheme 71: (A and B) Stereoselective nickel-catalyzed C–H difluoroalkylation; (C) late-stage functionalization...
Scheme 72: (A) Cu-mediated ortho-amination of oxalamides; (B) achieved scope, including derivatives obtained f...
Scheme 73: (A) Electro-oxidative copper-mediated amination of 8-aminoquinoline-derived amides; (B) achieved sc...
Scheme 74: (A and B) Cu(I)-mediated C–H amination with oximes; (C) derivatization using telmisartan (241) as s...
Scheme 75: (A and B) Cu-mediated amination of aryl amides using ammonia; (C) late-stage modification of proben...
Scheme 76: (A and B) Synthesis of purine nucleoside analogues using copper-mediated C(sp2)–H activation.
Scheme 77: (A) Copper-mediated annulation of acrylamide; (B) achieved scope, including the synthesis of the co...
Scheme 78: (A) Known bioactive compounds containing a naphthyl aryl ether motif; (B and C) copper-mediated eth...
Scheme 79: (A and B) Cu-mediated alkylation of N-oxide-heteroarenes; (C) late-stage modification.
Scheme 80: (A) Cu-mediated cross-dehydrogenative coupling of polyfluoroarenes and alkanes; (B) scope from know...
Scheme 81: (A) Known anticancer acrylonitrile compounds; (B and C) Copper-mediated cyanation of unactivated al...
Scheme 82: (A) Cu-mediated radiofluorination of 8-aminoquinoline-derived aryl amides; (B) achieved scope, incl...
Scheme 83: (A) Examples of natural β-carbolines; (B and C) an example of a zinc-catalyzed C–H functionalizatio...
Scheme 84: (A) Examples of anticancer α-aminophosphonic acid derivatives; (B and C) an example of a zinc-catal...
Beilstein J. Org. Chem. 2020, 16, 2739–2748, doi:10.3762/bjoc.16.224
Graphical Abstract
Scheme 1: Reaction of purine (2) with tetrakis(trifluoromethyl)-1,3-dithietane (1).
Figure 1: Crystal structure of 2a, with the thermal ellipsoids drawn at 30% probability.
Scheme 2: Reaction of 4-azabenzimidazole (3) with tetrakis(trifluoromethyl)-1,3-dithietane (1).
Scheme 3: Reaction of 5-azabenzimidazole (4) with 1.
Scheme 4: Reaction of adenine (5) and 2-fluoroadenine (6) with tetrakis(trifluoromethyl)-1,3-dithietane (1).
Scheme 5: Reaction of theophylline (7) with tetrakis(trifluoromethyl)-1,3-dithietane (1).
Figure 2: Crystal structure of 7a, with the thermal ellipsoids drawn at 30% probability.
Scheme 6: Probable mechanism of the reaction of tetrakis(trifluoromethyl)-1,3-dithietane (1) with compounds 2–...
Figure 3: Top: 19F NMR spectra of 3a acquired over a sample temperature range of 223–373 K. Left: Fitted plot...
Figure 4: DFT-optimized structures of the two rotamers of 3a. Left: Lower-energy rotamer. Right: Higher-energ...
Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147
Graphical Abstract
Figure 1: Concept of dual synergistic catalysis.
Figure 2: Classification of catalytic systems involving two catalysts.
Figure 3: General mechanism for the dual nickel/photoredox catalytic system.
Figure 4: General mechanisms for C–H activation catalysis involving different reoxidation strategies.
Figure 5: Indole synthesis via dual C–H activation/photoredox catalysis.
Figure 6: Proposed mechanism for the indole synthesis via dual catalysis.
Figure 7: Oxidative Heck reaction on arenes via the dual catalysis.
Figure 8: Proposed mechanism for the Heck reaction on arenes via dual catalysis.
Figure 9: Oxidative Heck reaction on phenols via the dual catalysis.
Figure 10: Proposed mechanism for the Heck reaction on phenols via dual catalysis.
Figure 11: Carbazole synthesis via dual C–H activation/photoredox catalysis.
Figure 12: Proposed mechanism for the carbazole synthesis via dual catalysis.
Figure 13: Carbonylation of enamides via the dual C–H activation/photoredox catalysis.
Figure 14: Proposed mechanism for carbonylation of enamides via dual catalysis.
Figure 15: Annulation of benzamides via the dual C–H activation/photoredox catalysis.
Figure 16: Proposed mechanism for the annulation of benzamides via dual catalysis.
Figure 17: Synthesis of indoles via the dual C–H activation/photoredox catalysis.
Figure 18: Proposed mechanism for the indole synthesis via dual catalysis.
Figure 19: General concept of dual catalysis merging C–H activation and photoredox catalysis.
Figure 20: The first example of dual catalysis merging C–H activation and photoredox catalysis.
Figure 21: Proposed mechanism for the C–H arylation with diazonium salts via dual catalysis.
Figure 22: Dual catalysis merging C–H activation/photoredox using diaryliodonium salts.
Figure 23: Direct arylation via the dual catalytic system reported by Xu.
Figure 24: Direct arylation via dual catalytic system reported by Balaraman.
Figure 25: Direct arylation via dual catalytic system reported by Guo.
Figure 26: C(sp3)–H bond arylation via the dual Pd/photoredox catalytic system.
Figure 27: Acetanilide derivatives acylation via the dual C–H activation/photoredox catalysis.
Figure 28: Proposed mechanism for the C–H acylation with α-ketoacids via dual catalysis.
Figure 29: Acylation of azobenzenes via the dual catalysis C–H activation/photoredox.
Figure 30: C2-acylation of indoles via the dual C–H activation/photoredox catalysis.
Figure 31: Proposed mechanism for the C2-acylation of indoles with aldehydes via dual catalysis.
Figure 32: C2-acylation of indoles via the dual C–H activation/photoredox catalysis.
Figure 33: Perfluoroalkylation of arenes via the dual C–H activation/photoredox catalysis.
Figure 34: Proposed mechanism for perfluoroalkylation of arenes via dual catalysis.
Figure 35: Sulfonylation of 1-naphthylamides via the dual C–H activation/photoredox catalysis.
Figure 36: Proposed mechanism for sulfonylation of 1-naphthylamides via dual catalysis.
Figure 37: meta-C–H Alkylation of arenes via visible-light metallaphotocatalysis.
Figure 38: Alternative procedure for meta-C–H alkylation of arenes via metallaphotocatalysis.
Figure 39: Proposed mechanism for meta-C–H alkylation of arenes via metallaphotocatalysis.
Figure 40: C–H borylation of arenes via visible-light metallaphotocatalysis.
Figure 41: Proposed mechanism for C–H borylation of arenes via visible-light metallaphotocatalysis.
Figure 42: Undirected C–H aryl–aryl cross coupling via dual gold/photoredox catalysis.
Figure 43: Proposed mechanism for the undirected C–H aryl–aryl cross-coupling via dual catalysis.
Figure 44: Undirected C–H arylation of (hetero)arenes via dual manganese/photoredox catalysis.
Figure 45: Proposed mechanism for the undirected arylation of (hetero)arenes via dual catalysis.
Figure 46: Photoinduced C–H arylation of azoles via copper catalysis.
Figure 47: Photo-induced C–H chalcogenation of azoles via copper catalysis.
Figure 48: Decarboxylative C–H adamantylation of azoles via dual cobalt/photoredox catalysis.
Figure 49: Proposed mechanism for the C–H adamantylation of azoles via dual catalysis.
Figure 50: General mechanisms for the “classical” (left) and Cu-free variant (right) Sonogoshira reaction.
Figure 51: First example of a dual palladium/photoredox catalysis for Sonogashira-type couplings.
Figure 52: Arylation of terminal alkynes with diazonium salts via dual gold/photoredox catalysis.
Figure 53: Proposed mechanism for the arylation of terminal alkynes via dual catalysis.
Figure 54: C–H Alkylation of alcohols promoted by H-atom transfer (HAT).
Figure 55: Proposed mechanism for the C–H alkylation of alcohols promoted by HAT.
Figure 56: C(sp3)–H arylation of latent nucleophiles promoted by H-atom transfer.
Figure 57: Proposed mechanism for the C(sp3)–H arylation of latent nucleophiles promoted by HAT.
Figure 58: Direct α-arylation of alcohols promoted by H-atom transfer.
Figure 59: Proposed mechanism for the direct α-arylation of alcohols promoted by HAT.
Figure 60: C–H arylation of amines via dual Ni/photoredox catalysis.
Figure 61: Proposed mechanism for the C–H arylation of amines via dual Ni/photoredox catalysis.
Figure 62: C–H functionalization of nucleophiles via excited ketone/nickel dual catalysis.
Figure 63: Proposed mechanism for the C–H functionalization enabled by excited ketones.
Figure 64: Selective sp3–sp3 cross-coupling promoted by H-atom transfer.
Figure 65: Proposed mechanism for the selective sp3–sp3 cross-coupling promoted by HAT.
Figure 66: Direct C(sp3)–H acylation of amines via dual Ni/photoredox catalysis.
Figure 67: Proposed mechanism for the C–H acylation of amines via dual Ni/photoredox catalysis.
Figure 68: C–H hydroalkylation of internal alkynes via dual Ni/photoredox catalysis.
Figure 69: Proposed mechanism for the C–H hydroalkylation of internal alkynes.
Figure 70: Alternative procedure for the C–H hydroalkylation of ynones, ynoates, and ynamides.
Figure 71: Allylic C(sp3)–H activation via dual Ni/photoredox catalysis.
Figure 72: Proposed mechanism for the allylic C(sp3)–H activation via dual Ni/photoredox catalysis.
Figure 73: Asymmetric allylation of aldehydes via dual Cr/photoredox catalysis.
Figure 74: Proposed mechanism for the asymmetric allylation of aldehydes via dual catalysis.
Figure 75: Aldehyde C–H functionalization promoted by H-atom transfer.
Figure 76: Proposed mechanism for the C–H functionalization of aldehydes promoted by HAT.
Figure 77: Direct C–H arylation of strong aliphatic bonds promoted by HAT.
Figure 78: Proposed mechanism for the C–H arylation of strong aliphatic bonds promoted by HAT.
Figure 79: Direct C–H trifluoromethylation of strong aliphatic bonds promoted by HAT.
Figure 80: Proposed mechanism for the C–H trifluoromethylation of strong aliphatic bonds.
Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52
Graphical Abstract
Scheme 1: Chemical structure of the catalysts 1a and 1b and their catalytic application in CuAAC reactions.
Scheme 2: Synthetic route to the catalyst 11 and its catalytic application in CuAAC reactions.
Scheme 3: Synthetic route of dendrons, illustrated using G2-AMP 23.
Scheme 4: The catalytic application of CuYAu–Gx-AAA–SBA-15 in a CuAAC reaction.
Scheme 5: Synthetic route to the catalyst 36.
Scheme 6: Application of the catalyst 36 in CuAAC reactions.
Scheme 7: The synthetic route to the catalyst 45 and catalytic application of 45 in “click” reactions.
Scheme 8: Synthetic route to the catalyst 48 and catalytic application of 48 in “click” reactions.
Scheme 9: Synthetic route to the catalyst 58 and catalytic application of 58 in “click” reactions.
Scheme 10: Synthetic route to the catalyst 64 and catalytic application of 64 in “click” reactions.
Scheme 11: Chemical structure of the catalyst 68 and catalytic application of 68 in “click” reactions.
Scheme 12: Chemical structure of the catalyst 69 and catalytic application of 69 in “click” reactions.
Scheme 13: Synthetic route to, and chemical structure of the catalyst 74.
Scheme 14: Application of the cayalyst 74 in “click” reactions.
Scheme 15: Synthetic route to, and chemical structure of the catalyst 78 and catalytic application of 78 in “c...
Scheme 16: Synthetic route to the catalyst 85.
Scheme 17: Application of the catalyst 85 in “click” reactions.
Scheme 18: Synthetic route to the catalyst 87 and catalytic application of 87 in “click” reactions.
Scheme 19: Chemical structure of the catalyst 88 and catalytic application of 88 in “click” reactions.
Scheme 20: Synthetic route to the catalyst 90 and catalytic application of 90 in “click” reactions.
Scheme 21: Synthetic route to the catalyst 96 and catalytic application of 96 in “click” reactions.
Scheme 22: Synthetic route to the catalyst 100 and catalytic application of 100 in “click” reactions.
Scheme 23: Synthetic route to the catalyst 102 and catalytic application of 23 in “click” reactions.
Scheme 24: Synthetic route to the catalysts 108–111.
Scheme 25: Catalytic application of 108–111 in “click” reactions.
Scheme 26: Synthetic route to the catalyst 121 and catalytic application of 121 in “click” reactions.
Scheme 27: Synthetic route to 125 and application of 125 in “click” reactions.
Scheme 28: Synthetic route to the catalyst 131 and catalytic application of 131 in “click” reactions.
Scheme 29: Synthetic route to the catalyst 136.
Scheme 30: Application of the catalyst 136 in “click” reactions.
Scheme 31: Synthetic route to the catalyst 141 and catalytic application of 141 in “click” reactions.
Scheme 32: Synthetic route to the catalyst 144 and catalytic application of 144 in “click” reactions.
Scheme 33: Synthetic route to the catalyst 149 and catalytic application of 149 in “click” reactions.
Scheme 34: Synthetic route to the catalyst 153 and catalytic application of 153 in “click” reactions.
Scheme 35: Synthetic route to the catalyst 155 and catalytic application of 155 in “click” reactions.
Scheme 36: Synthetic route to the catalyst 157 and catalytic application of 157 in “click” reactions.
Scheme 37: Synthetic route to the catalyst 162.
Scheme 38: Application of the catalyst 162 in “click” reactions.
Scheme 39: Synthetic route to the catalyst 167 and catalytic application of 167 in “click” reactions.
Scheme 40: Synthetic route to the catalyst 169 and catalytic application of 169 in “click” reactions.
Scheme 41: Synthetic route to the catalyst 172.
Scheme 42: Application of the catalyst 172 in “click” reactions.
Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253
Graphical Abstract
Figure 1: Different types of sulfonated materials as acid catalysts.
Scheme 1: Synthetic route of 3-methyl-1-sulfo-1H-imidazolium metal chloride ILs and their catalytic applicati...
Scheme 2: Synthetic route of 1,3-disulfo-1H-imidazolium transition metal chloride ILs and their catalytic app...
Scheme 3: Synthetic route of 1,3-disulfoimidazolium carboxylate ILs and their catalytic applications in the s...
Scheme 4: Synthetic route of [BiPy](HSO3)2Cl2 and [Dsim]HSO4 ILs and their catalytic applications for the syn...
Scheme 5: The catalytic applications of (C4(DABCO-SO3H)2·4Cl) IL for the synthesis of spiro-isatin derivative...
Scheme 6: The catalytic applications of (C4(DABCO-SO3H)2·4Cl) IL for the synthesis of bis 2-amino-4H-pyran de...
Scheme 7: The synthetic route of N,N-disulfo-1,1,3,3-tetramethylguanidinium carboxylate ILs and their catalyt...
Scheme 8: The catalytic application of 1-methyl-3-sulfo-1H-imidazolium tetrachloroferrate IL in the synthesis...
Scheme 9: The synthetic route of 3-sulfo-1H-imidazolopyrimidinium hydrogen sulfate IL and its catalytic appli...
Scheme 10: The results for the synthesis of bis(indolyl)methanes and di(bis(indolyl)methyl)benzenes in the pre...
Scheme 11: The catalytic applications of 1-(1-sulfoalkyl)-3-methylimidazolium chloride acidic ILs for the hydr...
Scheme 12: The synthetic route of immobilized 1,4-diazabicyclo[2.2.2]octanesulfonic acid chloride on SiO2 and ...
Scheme 13: The catalytic application of a silica-bonded sulfoimidazolium chloride for the synthesis of 12-aryl...
Scheme 14: The synthetic route of the SBA-15-Ph-SO3H and its catalytic applications for the synthesis of 2H-in...
Scheme 15: The synthetic route for heteropolyanion-based ionic liquids immobilized on mesoporous silica SBA-15...
Scheme 16: Some mechanism aspects of SSA catalyst for the protection of amine derivatives.
Scheme 17: The synthetic route for MWCNT-SO3H and its catalytic application for the synthesis of N-substituted...
Scheme 18: The sulfonic acid-functionalized polymers (P-SO3H) covalently grafted on multi-walled carbon nanotu...
Scheme 19: The transesterification reaction in the presence of S-MWCNTs.
Scheme 20: The synthetic route for the new hypercrosslinked supermicroporous polymer via the Friedel–Crafts al...
Scheme 21: The synthetic route for a new microporous copolymer via the Friedel–Crafts alkylation reaction of t...
Scheme 22: The synthetic route for sulfonated polynaphthalene and its catalytic application for the amidoalkyl...
Scheme 23: The synthetic route of the acidic carbon material and its catalytic application in the etherificatio...
Scheme 24: The synthetic route of the acidic carbon materials and their catalytic applications for the esterif...
Scheme 25: The sulfonated MWCNTs.
Scheme 26: The sulfonated nanoscaled diamond powder for the dehydration of D-xylose into furfural.
Scheme 27: The synthetic route and catalytic application of the GR-SO3H.
Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179
Graphical Abstract
Figure 1: Depiction of the energy levels of a typical organic molecule and the photophysical processes it can...
Figure 2: General catalytic cycle of a photocatalyst in a photoredox organocatalysed reaction. [cat] – photoc...
Figure 3: Structures and names of the most common photocatalysts encountered in the reviewed literature.
Figure 4: General example of a reductive quenching catalytic cycle. [cat] – photocatalyst, [cat]* – photocata...
Figure 5: General example of an oxidative quenching catalytic cycle. [cat] – photocatalyst, [cat]* – photocat...
Scheme 1: Oxidative coupling of aldehydes and amines to amides using acridinium salt photocatalysis.
Figure 6: Biologically active molecules containing a benzamide linkage.
Scheme 2: The photocatalytic reduction of amino acids to produce the corresponding free or protected amines.
Scheme 3: The organocatalysed photoredox base-mediated oxidation of thiols to disulfides.
Scheme 4: C-Terminal modification of peptides and proteins using organophotoredox catalysis.
Scheme 5: The reduction and aryl coupling of aryl halides using a doubly excited photocatalyst (PDI).
Figure 7: Mechanism for the coupling of aryl halides using PDI, which is excited sequentially by two photons.
Scheme 6: The arylation of five-membered heteroarenes using arenediazonium salts under organophotoredox condi...
Scheme 7: The C–H (hetero)arylation of five-membered heterocycles under Eosin Y photocatalysis.
Scheme 8: The C–H sulfurisation of imidazoheterocycles using Eosin B-catalyzed photochemical methods.
Scheme 9: The introduction of the thiocyanate group using Eosin Y photocatalysis.
Scheme 10: Sulfonamidation of pyrroles using oxygen as the terminal oxidant.
Scheme 11: DDQ-catalysed C–H amination of arenes and heteroarenes.
Scheme 12: Photoredox-promoted radical Michael addition reactions of allylic or benzylic carbons.
Figure 8: Proposed mechanistic rationale for the observed chemoselectivities.
Scheme 13: The photocatalytic manipulation of C–H bonds adjacent to amine groups.
Scheme 14: The perylene-catalysed organophotoredox tandem difluoromethylation–acetamidation of styrene-type al...
Figure 9: Examples of biologically active molecules containing highly functionalised five membered heterocycl...
Scheme 15: The [3 + 2]-cycloaddition leading to the formation of pyrroles, through the reaction of 2H-azirines...
Figure 10: Proposed intermediate that determines the regioselectivity of the reaction.
Figure 11: Comparison of possible pathways of reaction and various intermediates involved.
Scheme 16: The acridinium salt-catalysed formation of oxazoles from aldehydes and 2H-azirines.
Scheme 17: The synthesis of oxazolines and thiazolines from amides and thioamides using organocatalysed photor...
Figure 12: Biologically active molecules on the market containing 1,3,4-oxadiazole moieties.
Scheme 18: The synthesis of 1,3,4-oxadiazoles from aldehyde semicarbazones using Eosin Y organophotocatalysis.
Scheme 19: The dimerization of primary thioamides to 1,2,4-thiadiazoles catalysed by the presence of Eosin Y a...
Scheme 20: The radical cycloaddition of o-methylthioarenediazonium salts and substituted alkynes towards the f...
Scheme 21: The dehydrogenative cascade reaction for the synthesis of 5,6-benzofused heterocyclic systems.
Figure 13: Trifluoromethylated version of compounds which have known biological activities.
Scheme 22: Eosin Y-catalysed photoredox formation of 3-substituted benzimidazoles.
Scheme 23: Oxidation of dihydropyrimidines by atmospheric oxygen using photoredox catalysis.
Scheme 24: Photoredox-organocatalysed transformation of 2-substituted phenolic imines to benzoxazoles.
Scheme 25: Visible light-driven oxidative annulation of arylamidines.
Scheme 26: Methylene blue-photocatalysed direct C–H trifluoromethylation of heterocycles.
Scheme 27: Photoredox hydrotrifluoromethylation of terminal alkenes and alkynes.
Scheme 28: Trifluoromethylation and perfluoroalkylation of aromatics and heteroaromatics.
Scheme 29: The cooperative asymmetric and photoredox catalysis towards the functionalisation of α-amino sp3 C–...
Scheme 30: Organophotoredox-catalysed direct C–H amidation of aromatics.
Scheme 31: Direct C–H alkylation of heterocycles using BF3K salts. CFL – compact fluorescent lamp.
Figure 14: The modification of camptothecin, demonstrating the use of the Molander protocol in LSF.
Scheme 32: Direct C–H amination of aromatics using acridinium salts.
Scheme 33: Photoredox-catalysed nucleophilic aromatic substitution of nucleophiles onto methoxybenzene derivat...
Scheme 34: The direct C–H cyanation of aromatics with a focus on its use for LSF.
Beilstein J. Org. Chem. 2017, 13, 2416–2427, doi:10.3762/bjoc.13.239
Graphical Abstract
Figure 1: a) Detailed supramolecular packing of a gabapentin–Er network; b) view along the b-axis of the supr...
Figure 2: a) Mechanochemical reactivity between the excipient MgO and carboxylic acid NSAID molecules; b) NSA...
Figure 3: Mechanochemical reaction to form Cu3(BTC)2 and the structure of Cu3(BTC)2·(HKUST-1) as reported by ...
Figure 4: Mechanochemical syntheses of coordination polymers from ZnO and fumaric acid. Reprinted with permis...
Figure 5: Mechanochemical synthesis of pillared MOFs from ZnO, fumaric acid and two auxiliary ligands (bipy a...
Figure 6: a) Synthesis of ZIF-8; b) fragment of the crystal structure of ZIF-8. Reprinted with permission fro...
Figure 7: a) Mechanochemical reaction of salicylic acid with Bi2O3 yielding bismuth mono-, di- and trisalicyl...
Beilstein J. Org. Chem. 2017, 13, 1524–1532, doi:10.3762/bjoc.13.152
Graphical Abstract
Scheme 1: Arylation of zinc meso-(bromophenyl)porphyrinates 1, 2 with benzothiazole and benzoxazole.
Scheme 2: Attempts of the arylation of zinc meso-(bromophenyl)porphyrinates 1 and 2 with benzoxazole and benz...
Scheme 3: Arylation of zinc meso-(bromophenyl)porphyrinates 1, 2 with benzothiazole, benzoxazole, N-methylben...
Scheme 4: Plausible action of palladium and copper catalysts with transmetalation step.
Scheme 5: Dirylation of zinc di-meso-(bromophenyl)porphyrinates 10–12 with benzothiazole, benzoxazole and N-m...
Scheme 6: Polyarylation of zinc tetrakis-meso-(bromophenyl)porphyrinate 18 with benzoxazole.
Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9
Graphical Abstract
Figure 1: Typical pilot scale single screw extruder (left) and a laboratory scale twin screw extruder (right)....
Figure 2: PTFE screw employed in single screw extrusion, with increasing root diameter (RD) from 45 mm to 95 ...
Figure 3: Modulated stainless steel intermeshing co-rotating screws employed typically in twin screw extrusio...
Scheme 1: Polymerisation of styrene using s-BuLi as an initiator.
Scheme 2: Telescoping process of the formation of polystyrene, followed by post polymerisation functionalisat...
Scheme 3: Proposed mechanism for the branching of polylactide. Adapted from [23].
Scheme 4: Chemical reaction between isocyanate and an alcohol to form polyurethane.
Figure 4: Representative diagram explaining the process involved in step growth polymerisation, which involve...
Scheme 5: Generic polycondensation reaction to produce polyamides.
Figure 5: Comparison of choline chloride/D-fructose DES prepared via twin screw extrusion (left) and conventi...
Scheme 6: Synthesis of HKUST-1, ZIF-8 and Al(fumarate)OH by twin screw extrusion. Adapted from [2].
Figure 6: Synthesis of Ni(NCS)2(PPh3)2 and [Ni(salen)] by twin screw extrusion. Adapted from [2].
Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14
Graphical Abstract
Figure 1: Photographs of Howard E. Zimmerman (July 5, 1926–February 12, 2012) (left) and Jane Zimmerman (née ...
Figure 2: (a) Schematic double helix fully saturated with intercalator (in purple) according to the neighbor ...
Figure 3: Bismethidium molecular tweezer 3 proposed as a graduate student at Columbia University, which was q...
Figure 4: Adenine 8 recognition by carboxylic acid containing tweezer 9 and a component analysis showing “com...
Figure 5: The first determination of the cost of freezing single bond rotations in a host–guest complex.
Figure 6: Glycouril-based molecular clip 16 and 17 developed by Nolte, an example of Harmata’s chiral Kagan-e...
Figure 7: Macrocyclic diacridines and dinaphthalene and the intercalation complexes they may form with one ch...
Figure 8: (a) Hairpin structure of CUGexp seen in (CUG)12. (b) U–U or T–T mismatches with no inter-strand hyd...
Figure 9: (a) CTG trinucleotide repeat expansion in DMPK gene produces expanded transcripts, one which CUGexp...
Beilstein J. Org. Chem. 2014, 10, 1999–2012, doi:10.3762/bjoc.10.208
Graphical Abstract
Figure 1: Structures of RF and its photoproducts.
Figure 2: A general scheme for the photodegradation of RF in aqueous solution.
Figure 3: log k–pH profiles for the photolysis of RF in aqueous solution using UV light (∆) and visible light...
Figure 4: log k–pH profiles for the photolysis of FMF (10−4 M) in alkaline solution under aerobic (○) and ana...
Figure 5: k'–pH profiles for the photolysis of FMF (10−4 M) in acidic solution under aerobic (○) and anaerobi...
Figure 6: Plots of k` versus pH for phosphate (▲) and sulfate (●) anion-catalyzed photodegradation of RF (5 ×...
Figure 7: log kobs–pH profiles for the photolysis of RF (5 × 10−5 M) in 0.1–0.5 M borate buffer. Experimental...
Figure 8: log kobs–pH profiles for the photolysis of RF (5 × 10−5 M) in 0.2–1.0 M citrate buffer. Experimenta...
Figure 9: k'–pH profile for the photolysis of RF (5 × 10−5 M) in the presence of CF (0.5–2.5 × 10−4 M). Exper...
Beilstein J. Org. Chem. 2013, 9, 2821–2833, doi:10.3762/bjoc.9.317
Graphical Abstract
Figure 1: Unique structural features of (−)-isosteviol.
Figure 2: Triphenylene ketal based on (−)-isosteviol.
Figure 3: Structural features of triptycene derivatives.
Scheme 1: Functionalization of triphenylene ketal 2a.
Figure 4: Hexaammoniumtriptycene hexachloride 4 and 15-oxo-derivatives 5a–c of (–)-isosteviol.
Scheme 2: Quinoxalines based on diketone 5b.
Scheme 3: Condensation of 5b with hexaammoniumtriptycene hexachloride.
Figure 5: Molecular modelling structures (Spartan ’08 V1.0.0) of (a) all-syn-8 and (b) anti,anti,syn-8.
Scheme 4: Synthesis of nitrobenzylic ester derivatives 10 and 11, starting from (−)-isosteviol 1.
Scheme 5: Condensation of the nitrobenzyl esters 10 and 11 with hexaammoniumtriptycene hexachloride 4.
Scheme 6: Hydrogenolysis to tricarboxylic acid all-syn-16.
Scheme 7: Alkylation of all-syn-16 renders terminal alkene all-syn-17.
Figure 6: (a) Top view on the molecular structure of all-syn-17 with the terminal alkene fragments labelled i...
Scheme 8: Alkylation of (−)-isosteviol diketone 9 with 5-bromo-1-pentene.
Scheme 9: Direct synthesis of alkylated triptycene 17 by condensation of 18 with hexaammoniumtriptycene hexac...
Scheme 10: Olefin metathesis of all-syn-17.
Figure 7: Extracts of the 13C NMR spectra of starting material and product.
Figure 8: Molecular modelling structure (MacroModel 9.3.5) of collapsed 19, (a) top view; (b) side view.
Figure 9: Screening of aromatic analytes with affinity materials 3, 7, 8, 17 and 19.
Figure 10: Primary data of anti,anti,syn-8 and a [3 + 2] cage compound (increasing pseudocumene concentrations...
Figure 11: Screening of protic analytes with affinity materials 3, 8, 14 and 15.