Search for "metal catalysis" in Full Text gives 128 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2023, 19, 1055ā1145, doi:10.3762/bjoc.19.81
Graphical Abstract
Figure 1: Oxidative and reductive activations of organic compounds harvesting photoredox catalysis.
Figure 2: General catalytic cycles of radical ion conPET (left) and radical ion e-PRC (right).
Figure 3: āBeginnerās guideā: comparison between advantages, capacities, and prospectives of conPET and PEC.
Figure 4: A) conPET reductive dehalogenation of aryl halides with PDI. B) Reductive CāH arylation with pyrrol...
Figure 5: A) Chromoselective mono- and disubstitution or polybrominated pyrimidines with pyrroles. B) Sequent...
Figure 6: A) Synthesis of pyrrolo[1,2-a]quinolines. B) Synthesis of ullazines.
Figure 7: A) Reductive phosphorylation of aryl halides via conPET. B) Selected examples from the substrate sc...
Figure 8: A) Reductive dehalogenation of aryl halides via conPET and selected examples from the substrate sco...
Figure 9: A) Reductive CāH arylation of aryl halides via conPET (top) and selected examples from the substrat...
Figure 10: A) Reductive hydrodehalogenation of aryl halides with Mes-Acr-BF4. B) Selected examples from the su...
Figure 11: A) Reductive hydrodechlorination of aryl chlorides with 4-DPAIPN. B) Proposed formation of CO2ā¢ā. C...
Figure 12: A) Reductive conPET borylation with 3CzEPAIPN (top) and selected examples from the substrate scope ...
Figure 13: Scale-up of conPET phosphorylation with 3CzEPAIPN.
Figure 14: A) Borylation of 1d. B) Characteristics and structure of PC1 with green and red parts showing the l...
Figure 15: A) Reductive CāH arylation scope with polysulfide conPET (top) and selected examples from the subst...
Figure 16: Scale-up of A) CāH arylation and B) dehaloborylation with polysulfide photocatalysis in continuous-...
Figure 17: A) Formation of [Ir1]0 and [Ir2]0 upon PET between [Ir1]+ and Et3N. B) Mechanism of multi-photon ta...
Figure 18: A) Reductive hydrodehalogenation of aryl halides via multi-photon tandem photocatalysis. B) Selecte...
Figure 19: A) Carbonylative amidation of aryl halides in continuous flow. B) Selected examples from the substr...
Figure 20: A) General scheme for reductive (RQ) and oxidative quenching (OQ) protocols using [FeIII(btz)3](PF6)...
Figure 21: A) Carbonylative amidation of alkyl iodides with [IrIII(ppy)2(dtbbpy)]PF6. B) Selected examples fro...
Figure 22: A) Carboxylative CāN bond cleavage in cyclic amines. B) Selected examples from the substrate scope....
Figure 23: A) Formal reduction of alkenes to alkanes via transfer hydrogenation. B) Selected examples from the...
Figure 24: A) Birch-type reduction of benzenes with PMP-BPI. B) Selected examples from the substrate scope (sc...
Figure 25: Proposed mechanism of the OHā mediated conPET Birch-type reduction of benzene via generation of sol...
Figure 26: Reductive detosylation of N-tosylated amides with Mes-Acr-BF4. B) Selected examples from the substr...
Figure 27: A) Reductive detosylation of N-tosyl amides by dual PRC. B) Selected examples from the substrate sc...
Figure 28: A) Mechanism of the dual PRC based on PET between [Cu(dap)2]+ and DCA. B) Mechanism of the dual PRC...
Figure 29: A) NāO bond cleavage in Weinreb amides with anthracene. B) NāO bond cleavage in Weinreb amides rely...
Figure 30: A) Pentafluorosulfanylation and fluoride elimination. B) Mechanism of the pentafluorosulfanylation ...
Figure 31: A) α-Alkoxypentafluorosulfanylation (top) and selected examples from the substrate scope (bottom). ...
Figure 32: A) Oxidative amination of arenes with azoles catalyzed by N-Ph PTZ. B) Selected examples from the s...
Figure 33: A) C(sp3)āH bond activation by HAT via chloride oxidation by *N-Ph PTZā¢+. B) Proposed mechanism for...
Figure 34: A) Recycling e-PRC CāH azolation of electron-rich arenes with pyrazoles using Mes-Acr+ as a photoca...
Figure 35: A) Radical ion e-PRC direct oxidation of unactivated arenes using TAC+ as an electro-activated phot...
Figure 36: A) Radical ion e-PRC direct oxidation of unactivated arenes using TPA as an electro-activated photo...
Figure 37: Proposed mechanism (top) and mode of preassembly (bottom).
Figure 38: A) Possible preassemblies of reactive (left) vs unreactive (right) arenes. B) Calculated spin densi...
Figure 39: A) Recycling e-PRC C(sp2 )āH acetoxylation of arenes using DDQ as a photocatalyst. B) Proposed cata...
Figure 40: Gram scale hydroxylation of benzene in a recirculated flow setup.
Figure 41: A) Radical ion e-PRC vicinal diamination of alkylarenes using TAC+ as an electro-activated photocat...
Figure 42: A) Sequential oxygenation of multiple adjacent CāH bonds under radical ion e-PRC using TAC+ as an e...
Figure 43: A) Enantioselective recycling e-PRC cyanation of benzylic CāH bonds using ADQS as photocatalyst. B)...
Figure 44: Proposed tandem mechanism by Xu and co-workers.
Figure 45: A) Enantioselective recycling e-PRC decarboxylative cyanation using Cu(acac)2, Ce(OTf)3 and a box l...
Figure 46: A) Enantioselective recycling e-PRC benzylic cyanation using Cu(MeCN)4BF4, box ligand and anthraqui...
Figure 47: A) Radical ion e-PRC acetoxyhydroxylation of aryl olefins using TAC+ as an electro-activated photoc...
Figure 48: Selected examples from the substrate scope.
Figure 49: Photoelectrochemical acetoxyhydroxylation in a recirculated flow setup.
Figure 50: A) Radical ion e-PRC aminooxygenation of aryl olefins using TAC+ as an electro-activated photocatal...
Figure 51: A) Recycling e-PRC CāH alkylation of heteroarenes with organic trifluoroborates using Mes-Acr+ as p...
Figure 52: A) Recycling e-PRC decarboxylative CāH alkylation of heteroarenes using CeCl3Ā·7H2O as catalyst. B) ...
Figure 53: A) Recycling e-PRC decarboxylative CāH alkylation of heteroarenes using Fe(NH4)2(SO4)2Ā·6H2O as cata...
Figure 54: A) Recycling e-PRC CāH alkylation of heteroarenes with alkyl oxalates and 4CzIPN as photocatalyst. ...
Figure 55: A) Recycling e-PRC decarboxylative CāH carbamoylation of heteroarenes using 4CzIPN as photocatalyst...
Figure 56: A) Photoelectrochemical HAT-mediated hydrocarbon activation via the chlorine radical. B) Proposed m...
Figure 57: A) Selected examples from the substrate scope. B) Gram and decagram scale semi-continuous flow PEC ...
Figure 58: A) Photoelectrochemical HAT-mediated dehydrogenative coupling of benzothiazoles with aliphatic CāH ...
Figure 59: A) Photoelectrochemical HAT activation of ethers using electro-activated TAC+ as photocatalyst. B) ...
Figure 60: Selected examples from the substrate scope.
Figure 61: A) Photoelectrochemical HAT-mediated synthesis of alkylated benzimidazo-fused isoquinolinones using...
Figure 62: A) Decoupled photoelectrochemical cerium-catalyzed oxydichlorination of alkynes using CeCl3 as cata...
Figure 63: Proposed decoupled photoelectrochemical mechanism.
Figure 64: A) Decoupled photoelectrochemical ring-opening bromination of tertiary cycloalkanols using MgBr2 as...
Figure 65: A) Recycling e-PRC ring-opening functionalization of cycloalkanols using CeCl3 as catalyst. B) Prop...
Figure 66: Selected examples from the substrate scope of the PEC ring-opening functionalization.
Figure 67: A) Radical ion e-PRC reduction of chloro- and bromoarenes using DCA as catalyst and various accepto...
Figure 68: A) Screening of different phthalimide derivatives as catalyst for the e-PRC reduction of aryl halid...
Figure 69: Screening of different organic catalysts for the e-PRC reduction of trialkylanilium salts.
Figure 70: A) e-PRC reduction of phosphonated phenols and anilinium salts. B) Selected examples from the subst...
Figure 71: A) ConPET and e-PRC reduction of 4-bromobenzonitrile using a naphthalene diimide (NDI) precatalyst ...
Figure 72: A) Radical ion e-PRC reduction of phosphinated aliphatic alcohols with n-BuO-NpMI as catalyst. B) C...
Figure 73: Selected examples from the substrate scope.
Figure 74: A) Recycling e-PRC reductive dimerization of benzylic chlorides using a [Cu2] catalyst. B) Proposed...
Figure 75: A) Decoupled photoelectrochemical CāH alkylation of heteroarenes through deamination of Katritzky s...
Figure 76: Proposed mechanism by Chen and co-workers.
Beilstein J. Org. Chem. 2023, 19, 956ā981, doi:10.3762/bjoc.19.72
Graphical Abstract
Scheme 1: First organocatalyzed asymmetric aza-FriedelāCrafts reaction.
Scheme 2: Aza-FriedelāCrafts reaction between indoles and cyclic ketimines.
Scheme 3: Aza-FriedelāCrafts reaction utilizing trifluoromethyldihydrobenzoazepinoindoles as electrophiles.
Scheme 4: Aza-FriedelāCrafts reaction utilizing cyclic N-sulfimines as electrophiles.
Scheme 5: Aza-FriedelāCrafts reaction involving N-unprotected imino ester as electrophile.
Scheme 6: Aza-FriedelāCrafts and lactonization cascade.
Scheme 7: One-pot oxidation and aza-FriedelāCrafts reaction.
Scheme 8: C1 and C2-symmetric phosphoric acids as catalysts.
Scheme 9: Aza-FriedelāCrafts reaction using Nps-iminophosphonates as electrophiles.
Scheme 10: Aza-FriedelāCrafts reaction between indole and α-iminophosphonate.
Scheme 11: [2.2]-Paracyclophane-derived chiral phosphoric acids as catalyst.
Scheme 12: Aza-FriedelāCrafts reaction through ring opening of sulfamidates.
Scheme 13: Isoquinoline-1,3(2H,4H)-dione scaffolds as electrophiles.
Scheme 14: Functionalization of the carbocyclic ring of substituted indoles.
Scheme 15: Aza-FriedelāCrafts reaction between unprotected imines and aza-heterocycles.
Scheme 16: Anilines and α-naphthols as potential nucleophiles.
Scheme 17: Solvent-controlled regioselective aza-FriedelāCrafts reaction.
Scheme 18: Generating central and axial chirality via aza-FriedelāCrafts reaction.
Scheme 19: Reaction between indoles and racemic 2,3-dihydroisoxazol-3-ol derivatives.
Scheme 20: Exploiting 5-aminoisoxazoles as nucleophiles.
Scheme 21: Reaction between unsubstituted indoles and 3-alkynylated 3-hydroxy-1-oxoisoindolines.
Scheme 22: Synthesis of unnatural amino acids bearing an aza-quaternary stereocenter.
Scheme 23: Atroposelective aza-FriedelāCrafts reaction.
Scheme 24: Coupling of 5-aminopyrazole and 3H-indol-3-ones.
Scheme 25: Pyrophosphoric acid-catalyzed aza-FriedelāCrafts reaction on phenols.
Scheme 26: Squaramide-assisted aza-FriedelāCrafts reaction.
Scheme 27: Thiourea-catalyzed aza-FriedelāCrafts reaction.
Scheme 28: Squaramide-catalyzed reaction between β-naphthols and benzothiazolimines.
Scheme 29: Thiourea-catalyzed reaction between β-naphthol and isatin-derived ketamine.
Scheme 30: Quinine-derived molecule as catalyst.
Scheme 31: Cinchona alkaloid as catalyst.
Scheme 32: aza-FriedelāCrafts reaction by phase transfer catalyst.
Scheme 33: Disulfonamide-catalyzed reaction.
Scheme 34: Heterogenous thiourea-catalyzed aza-FriedelāCrafts reaction.
Scheme 35: Total synthesis of (+)-gracilamine.
Scheme 36: Total synthesis of (ā)-fumimycin.
Beilstein J. Org. Chem. 2023, 19, 820ā863, doi:10.3762/bjoc.19.62
Graphical Abstract
Figure 1: Representative examples of bioactive natural products and FDA-approved drugs containing a pyridine ...
Scheme 1: Classical and traditional methods for the synthesis of functionalized pyridines.
Scheme 2: Rare earth metal (Ln)-catalyzed pyridine CāH alkylation.
Scheme 3: Pd-catalyzed CāH alkylation of pyridine N-oxide.
Scheme 4: CuI-catalyzed CāH alkylation of N-iminopyridinium ylides with tosylhydrazones (A) and a plausible r...
Scheme 5: Zirconium complex-catalyzed pyridine CāH alkylation.
Scheme 6: Rare earth metal-catalyzed pyridine CāH alkylation with nonpolar unsaturated substrates.
Scheme 7: Heterobimetallic RhāAl complex-catalyzed ortho-CāH monoalkylation of pyridines.
Scheme 8: Mono(phosphinoamido)-rare earth complex-catalyzed pyridine CāH alkylation.
Scheme 9: Rhodium-catalyzed pyridine CāH alkylation with acrylates and acrylamides.
Scheme 10: NiāAl bimetallic system-catalyzed pyridine CāH alkylation.
Scheme 11: Iridium-catalyzed pyridine CāH alkylation.
Scheme 12: para-C(sp2)āH Alkylation of pyridines with alkenes.
Scheme 13: Enantioselective pyridine CāH alkylation.
Scheme 14: Pd-catalyzed C2-olefination of pyridines.
Scheme 15: Ru-catalyzed C-6 (C-2)-propenylation of 2-arylated pyridines.
Scheme 16: CāH addition of allenes to pyridines catalyzed by half-sandwich Sc metal complex.
Scheme 17: Pd-catalyzed stereodivergent synthesis of alkenylated pyridines.
Scheme 18: Pd-catalyzed ligand-promoted selective C3-olefination of pyridines.
Scheme 19: Mono-N-protected amino acids in Pd-catalyzed C3-alkenylation of pyridines.
Scheme 20: Amide-directed and rhodium-catalyzed C3-alkenylation of pyridines.
Scheme 21: Bimetallic NiāAl-catalyzed para-selective alkenylation of pyridine.
Scheme 22: Arylboronic ester-assisted pyridine direct CāH arylation.
Scheme 23: Pd-catalyzed CāH arylation/benzylation with toluene.
Scheme 24: Pd-catalyzed pyridine CāH arylation with potassium aryl- and heteroaryltrifluoroborates.
Scheme 25: Transient activator strategy in pyridine CāH biarylation.
Scheme 26: Ligand-promoted C3-arylation of pyridine.
Scheme 27: Pd-catalyzed arylation of nicotinic and isonicotinic acids.
Scheme 28: Iron-catalyzed and imine-directed CāH arylation of pyridines.
Scheme 29: Pdā(bipy-6-OH) cooperative system-mediated direct pyridine C3-arylation.
Scheme 30: Pd-catalyzed pyridine N-oxide CāH arylation with heteroarylcarboxylic acids.
Scheme 31: Pd-catalyzed CāH cross-coupling of pyridine N-oxides with five-membered heterocycles.
Scheme 32: Cu-catalyzed dehydrative biaryl coupling of azine(pyridine) N-oxides and oxazoles.
Scheme 33: Rh(III)-catalyzed cross dehydrogenative C3-heteroarylation of pyridines.
Scheme 34: Pd-catalyzed C3-selective arylation of pyridines.
Scheme 35: Rhodium-catalyzed oxidative CāH annulation of pyridines to quinolines.
Scheme 36: Rhodium-catalyzed and NHC-directed CāH annulation of pyridine.
Scheme 37: Ni/NHC-catalyzed regio- and enantioselective CāH cyclization of pyridines.
Scheme 38: Rare earth metal-catalyzed intramolecular CāH cyclization of pyridine to azaindolines.
Scheme 39: Rh-catalyzed alkenylation of bipyridine with terminal silylacetylenes.
Scheme 40: Rollover cyclometallation in Rh-catalyzed pyridine CāH functionalization.
Scheme 41: Rollover pathway in Rh-catalyzed CāH functionalization of N,N,N-tridentate chelating compounds.
Scheme 42: Pd-catalyzed rollover pathway in bipyridine-6-carboxamides CāH arylation.
Scheme 43: Rh-catalyzed C3-acylmethylation of bipyridine-6-carboxamides with sulfoxonium ylides.
Scheme 44: Rh-catalyzed CāH functionalization of bipyridines with alkynes.
Scheme 45: Rh-catalyzed CāH acylmethylation and annulation of bipyridine with sulfoxonium ylides.
Scheme 46: Iridium-catalyzed C4-borylation of pyridines.
Scheme 47: C3-Borylation of pyridines.
Scheme 48: Pd-catalyzed regioselective synthesis of silylated dihydropyridines.
Beilstein J. Org. Chem. 2023, 19, 700ā718, doi:10.3762/bjoc.19.51
Graphical Abstract
Figure 1: Dibenzo[b,f]azepine (1a), -oxepine (1b) and -thiepine (1c) as examples of dibenzo[b,f]heteropines (1...
Figure 2: Selected pharmaceuticals with the dibenzo[b,f]azepine skeleton.
Figure 3: Examples of 10,11-dihydrodibenzo[b,f]azepine-based ligands.
Figure 4: The dibenzo[b,f]azepine moiety in dyes with properties suitable for the use in organic light emitti...
Figure 5: Selective bioactive natural products (13ā18) containing the dibenzo[b,f]oxepine scaffold and Novart...
Scheme 1: Retrosynthetic approach to 5H-dibenzo[b,f]azepine (1a) from nitrotoluene (22).
Scheme 2: Oxidative coupling of o-nitrotoluene (22) and reduction of 2,2'-dinitrobibenzyl (21) to form 2,2'-d...
Scheme 3: Synthesis of 10,11-dihydro-5H-dibenzo[b,f]azepine (2a) via amine condensation.
Scheme 4: Catalytic reduction of 10,11-dihydro-5H-dibenzo[b,f]azepine (2a).
Scheme 5: The WagnerāMeerwein rearrangement of acridin-9-ylmethanol (23) into 5H-dibenzo[b,f]azepine (1a).
Scheme 6: Oxidative ring expansion of 2-(9-xanthenyl)malonates 24.
Scheme 7: Ring expansion via CāH functionalisation.
Scheme 8: The synthesis of fluorinated 5H-dibenzo[b,f]azepine 38 from isatin (32).
Scheme 9: The synthesis of substituted dibenzo[b,f]azepines 43 from indoles 39.
Scheme 10: Retrosynthetic pathways to dibenzo[b,f]azepines via BuchwaldāHartwig amination.
Scheme 11: Synthesis of dibenzo[b,f]oxepine 54 and -azepine 55 derivatives via (i) Heck reaction and (ii) Buch...
Scheme 12: Double BuchwaldāHartwig amination and thioetherification in the synthesis of tricyclic azepines 60 ...
Scheme 13: Double BuchwaldāHartwig amination towards substituted dibenzoazepines 62.
Scheme 14: Double BuchwaldāHartwig amination towards 10,11-dihydro-5H-dibenzo[b,f]azepine derivatives 71.
Scheme 15: One-pot Suzuki couplingāBuchwaldāHartwig amination.
Scheme 16: One-pot Rh/Pd-catalysed synthesis of dihydropyridobenzazepines.
Scheme 17: A retrosynthetic pathway to dibenzo[b,f]azepines via MizorokiāHeck reaction.
Scheme 18: One-pot domino Pd-catalyzed MizorokiāHeckāBuchwaldāHartwig synthesis of dibenzo[b,f]azepines.
Scheme 19: Dibenzo[b,f]thiapine and -oxepine synthesis via SNAr (thio)etherification, Wittig methylenation and...
Scheme 20: A retrosynthetic pathway to dibenzo[b,f]oxepines via Ullmann coupling.
Scheme 21: Ullmann-type coupling in dibenzo[b,f]oxepine synthesis.
Scheme 22: Wittig reaction and Ullmann coupling as key steps in dihydrobenz[b,f]oxepine synthesis.
Scheme 23: Pd-catalysed dibenzo[b,f]azepine synthesis via norbornene azepine intermediate 109.
Scheme 24: A simple representation of olefin metathesis resulting in transalkylidenation.
Scheme 25: Ring-closing metathesis as key step in the synthesis of dibenzo[b,f]heteropines.
Scheme 26: Alkyneāaldehyde metathesis in the synthesis of dibenzo[b,f]heteropines.
Scheme 27: Hydroarylation of 9-(2-alkynylphenyl)-9H-carbazole derivatives.
Scheme 28: Oxidative coupling of bisphonium ylide intermediate to give pacharin (13).
Scheme 29: Preparation of 10,11-dihydrodibenzo[b,f]heteropines via intramolecular Wurtz reaction.
Scheme 30: Phenol deprotonation and intramolecular etherification in the synthesis of bauhinoxepine J.
Figure 6: Functionalisation of dibenzo[b,f]azepine.
Scheme 31: Palladium-catalysed N-arylation of dibenzo[b,f]azepine.
Scheme 32: Cu- and Ni-catalysed N-arylation.
Scheme 33: N-Alkylation of dibenzo[b,f]azepine (1a) and dihydrodibenzo[b,f]azepine (2a).
Scheme 34: Preparation of methoxyiminosilbene.
Scheme 35: Synthesis of oxcarbazepine (153) from methoxy iminostilbene 151.
Scheme 36: Ring functionalisation of dihydrodibenzo[b,f]azepine.
Beilstein J. Org. Chem. 2023, 19, 593ā634, doi:10.3762/bjoc.19.44
Graphical Abstract
Scheme 1: General scheme depicting tandem reactions based on an asymmetric conjugate addition followed by an ...
Scheme 2: Cu-catalyzed tandem conjugate addition of R2Zn/aldol reaction with chiral acetals.
Scheme 3: Cu-catalyzed asymmetric desymmetrization of cyclopentene-1,3-diones using a tandem conjugate additi...
Scheme 4: Stereocontrolled assembly of dialkylzincs, cyclic enones, and sulfinylimines utilizing a Cu-catalyz...
Scheme 5: Cu-catalyzed tandem conjugate addition/Mannich reaction (A). Access to chiral isoindolinones and tr...
Scheme 6: Cu-catalyzed tandem conjugate addition/nitro-Mannich reaction (A) with synāanti or synāsyn selectiv...
Figure 1: Various chiral ligands utilized for the tandem conjugate addition/Michael reaction sequences.
Scheme 7: Cu-catalyzed tandem conjugate addition/Michael reaction: side-product formation with chalcone (A) a...
Scheme 8: Zn enolate trapping using allyl iodides (A), StorkāJung vinylsilane reagents (B), and allyl bromide...
Scheme 9: Cu-catalyzed tandem conjugate addition/acylation through Li R2Zn enolate (A). A four-component coup...
Scheme 10: Selected examples for the Cu-catalyzed tandem conjugate addition/trifluoromethylthiolation sequence....
Scheme 11: Zn enolates trapped by vinyloxiranes: synthesis of allylic alcohols.
Scheme 12: Stereoselective cyclopropanation of Mg enolates formed by ACA of Grignard reagents to chlorocrotona...
Scheme 13: Domino aldol reactions of Mg enolates formed from coumarin and chromone.
Scheme 14: Oxidative coupling of ACA-produced Mg enolates.
Scheme 15: Tandem ACA of Grignard reagents to enones and Mannich reaction.
Scheme 16: Diastereodivergent Mannich reaction of Mg enolates with differently N-protected imines.
Scheme 17: Tandem GrignardāACAāMannich using Taddol-based phosphine-phosphite ligands.
Scheme 18: Tandem reaction of Mg enolates with aminomethylating reagents.
Scheme 19: Tandem reaction composed of Grignard ACA to alkynyl enones.
Scheme 20: Rh/Cu-catalyzed tandem reaction of diazo enoates leading to cyclobutanes.
Scheme 21: Tandem Grignard-ACA of cyclopentenones and alkylation of enolates.
Scheme 22: Tandem ACA of Grignard reagents followed by enolate trapping reaction with onium compounds.
Scheme 23: Mg enolates generated from unsaturated lactones in reaction with activated alkenes.
Scheme 24: Lewis acid mediated ACA to amides and SN2 cyclization of a Br-appended enolate.
Scheme 25: Trapping reactions of aza-enolates with Michael acceptors.
Scheme 26: Si enolates generated by TMSOTf-mediated ACA of Grignard reagents and enolate trapping reaction wit...
Scheme 27: Trapping reactions of enolates generated from alkenyl heterocycles (A) and carboxylic acids (B) wit...
Scheme 28: Reactions of heterocyclic Mg enolates with onium compounds.
Scheme 29: Synthetic transformations of cycloheptatrienyl and benzodithiolyl substituents.
Scheme 30: Aminomethylation of Al enolates generated by ACA of trialkylaluminum reagents.
Scheme 31: Trapping reactions of enolates with activated alkenes.
Scheme 32: Alkynylation of racemic aluminum or magnesium enolates.
Scheme 33: Trapping reactions of Zr enolates generated by Cu-ACA of organozirconium reagents.
Scheme 34: Chloromethylation of Zr enolates using the VilsmeierāHaack reagent.
Scheme 35: Tandem conjugate borylation with subsequent protonation or enolate trapping by an electrophile.
Scheme 36: Tandem conjugate borylation/aldol reaction of cyclohexenones.
Scheme 37: Selected examples for the tandem asymmetric borylation/intramolecular aldol reaction; synthesis of ...
Scheme 38: Cu-catalyzed tandem methylborylation of α,β-unsaturated phosphine oxide in the presence of (R,Sp)-J...
Scheme 39: Cu-catalyzed tandem transannular conjugated borylation/aldol cyclization of macrocycles containing ...
Scheme 40: Stereoselective tandem conjugate borylation/Mannich cyclization: selected examples (A) and a multi-...
Scheme 41: Some examples of Cu-catalyzed asymmetric tandem borylation/aldol cyclization (A). Application to di...
Scheme 42: Atropisomeric P,N-ligands used in tandem conjugate borylation/aldol cyclization sequence.
Scheme 43: Selected examples for the enantioselective Cu-catalyzed borylation/intramolecular Michael addition ...
Scheme 44: Selected examples for the preparation of enantioenriched spiroindanes using a Cu-catalyzed tandem c...
Scheme 45: Enantioselective conjugate borylation of cyclobutene-1-carboxylic acid diphenylmethyl ester 175 wit...
Scheme 46: Cu-catalyzed enantioselective tandem conjugate silylation of α,β-unsaturated ketones with subsequen...
Scheme 47: Cu-catalyzed enantioselective tandem conjugate silylation of α,β-unsaturated ketones with subsequen...
Scheme 48: Cu-catalyzed tandem conjugate silylation/aldol condensation. The diastereoselectivity is controlled...
Scheme 49: Chiral Ru-catalyzed three-component coupling reaction.
Scheme 50: Rh-Phebox complex-catalyzed reductive cyclization and subsequent reaction with Michael acceptors th...
Scheme 51: Rh-catalyzed tandem asymmetric conjugate alkynylation/aldol reaction (A) and subsequent spiro-cycli...
Scheme 52: Rh-bod complex-catalyzed tandem asymmetric conjugate arylation/intramolecular aldol addition (A). S...
Scheme 53: Co-catalyzed CāH-bond activation/asymmetric conjugate addition/aldol reaction.
Scheme 54: (Diisopinocampheyl)borane-promoted 1,4-hydroboration of α,β-unsaturated morpholine carboxamides and...
Figure 2: Some examples of total syntheses that have been recently reviewed.
Scheme 55: Stereoselective synthesis of antimalarial prodrug (+)-artemisinin utilizing a tandem conjugate addi...
Scheme 56: Amphilectane and serrulatane diterpenoids: preparation of chiral starting material via asymmetric t...
Scheme 57: Various asymmetric syntheses of pleuromutilin and related compounds based on a tandem conjugate add...
Scheme 58: Total synthesis of glaucocalyxin A utilizing a tandem conjugate addition/acylation reaction sequenc...
Scheme 59: Installation of the exocyclic double bond using a tandem conjugate addition/aminomethylation sequen...
Scheme 60: Synthesis of the taxol core using a tandem conjugate addition/enolate trapping sequence with Vilsme...
Scheme 61: Synthesis of the tricyclic core of 12-epi-JBIR-23/24 utilizing a Rh-catalyzed asymmetric conjugate ...
Scheme 62: Total synthesis of (ā)-peyssonoside A utilizing a Cu-catalyzed enantioselective tandem conjugate ad...
Beilstein J. Org. Chem. 2023, 19, 487ā540, doi:10.3762/bjoc.19.38
Graphical Abstract
Figure 1: Ring-strain energies of homobicyclic and heterobicyclic alkenes in kcal molā1. a) [2.2.1]-Bicyclic ...
Figure 2: a) Exo and endo face descriptions of bicyclic alkenes. b) Reactivity comparisons for different β-at...
Scheme 1: Ni-catalyzed ring-opening/cyclization cascade of heterobicyclic alkenes 1 with alkyl propiolates 2 ...
Scheme 2: Ni-catalyzed ring-opening/cyclization cascade of heterobicyclic alkenes 8 with β-iodo-(Z)-propenoat...
Scheme 3: Ni-catalyzed two- and three-component difunctionalizations of norbornene derivatives 15 with alkyne...
Scheme 4: Ni-catalyzed intermolecular three-component difunctionalization of oxabicyclic alkenes 1 with alkyn...
Scheme 5: Ni-catalyzed intermolecular three-component carboacylation of norbornene derivatives 15.
Scheme 6: Photoredox/Ni dual-catalyzed coupling of 4-alkyl-1,4-dihydropyridines 31 with heterobicyclic alkene...
Scheme 7: Photoredox/Ni dual-catalyzed coupling of α-amino radicals with heterobicyclic alkenes 30.
Scheme 8: Cu-catalyzed rearrangement/allylic alkylation of 2,3-diazabicyclo[2.2.1]heptenes 47 with Grignard r...
Scheme 9: Cu-catalyzed aminoboration of bicyclic alkenes 1 with bis(pinacolato)diboron (B2pin2) (53) and O-be...
Scheme 10: Cu-catalyzed borylalkynylation of oxabenzonorbornadiene (30b) with B2pin2 (53) and bromoalkynes 62.
Scheme 11: Cu-catalyzed borylacylation of bicyclic alkenes 1.
Scheme 12: Cu-catalyzed diastereoselective 1,2-difunctionalization of oxabenzonorbornadienes 30 for the synthe...
Scheme 13: Fe-catalyzed carbozincation of heterobicyclic alkenes 1 with arylzinc reagents 74.
Scheme 14: Co-catalyzed addition of arylzinc reagents of norbornene derivatives 15.
Scheme 15: Co-catalyzed ring-opening/dehydration of oxabicyclic alkenes 30 via CāH activation of arenes.
Scheme 16: Co-catalyzed [3 + 2] annulation/ring-opening/dehydration domino reaction of oxabicyclic alkenes 1 w...
Scheme 17: Co-catalyzed enantioselective carboamination of bicyclic alkenes 1 via CāH functionalization.
Scheme 18: Ru-catalyzed cyclization of oxabenzonorbornene derivatives with propargylic alcohols for the synthe...
Scheme 19: Ru-catalyzed coupling of oxabenzonorbornene derivatives 30 with propargylic alcohols and ethers 106...
Scheme 20: Ru-catalyzed ring-opening/dehydration of oxabicyclic alkenes via the CāH activation of anilides.
Scheme 21: Ru-catalyzed of azabenzonorbornadiene derivatives with arylamides.
Scheme 22: Rh-catalyzed cyclization of bicyclic alkenes with arylboronate esters 118.
Scheme 23: Rh-catalyzed cyclization of bicyclic alkenes with dienyl- and heteroaromatic boronate esters.
Scheme 24: Rh-catalyzed domino lactonization of doubly bridgehead-substituted oxabicyclic alkenes with seconda...
Scheme 25: Rh-catalyzed domino carboannulation of diazabicyclic alkenes with 2-cyanophenylboronic acid and 2-f...
Scheme 26: Rh-catalyzed synthesis of oxazolidinone scaffolds 147 through a domino ARO/cyclization of oxabicycl...
Scheme 27: Rh-catalyzed oxidative coupling of salicylaldehyde derivatives 151 with diazabicyclic alkenes 130a.
Scheme 28: Rh-catalyzed reaction of O-acetyl ketoximes with bicyclic alkenes for the synthesis of isoquinoline...
Scheme 29: Rh-catalyzed domino coupling reaction of 2-phenylpyridines 165 with oxa- and azabicyclic alkenes 30....
Scheme 30: Rh-catalyzed domino dehydrative naphthylation of oxabenzonorbornadienes 30 with N-sulfonyl 2-aminob...
Scheme 31: Rh-catalyzed domino dehydrative naphthylation of oxabenzonorbornadienes 30 with arylphosphine deriv...
Scheme 32: Rh-catalyzed domino ring-opening coupling reaction of azaspirotricyclic alkenes using arylboronic a...
Scheme 33: Tandem Rh(III)/Sc(III)-catalyzed domino reaction of oxabenzonorbornadienes 30 with alkynols 184 dir...
Scheme 34: Rh-catalyzed asymmetric domino cyclization and addition reaction of 1,6-enynes 194 and oxa/azabenzo...
Scheme 35: Rh/Zn-catalyzed domino ARO/cyclization of oxabenzonorbornadienes 30 with phosphorus ylides 201.
Scheme 36: Rh-catalyzed domino ring opening/lactonization of oxabenzonorbornadienes 30 with 2-nitrobenzenesulf...
Scheme 37: Rh-catalyzed domino CāC/CāN bond formation of azabenzonorbornadienes 30 with aryl-2H-indazoles 210.
Scheme 38: Rh/Pd-catalyzed domino synthesis of indole derivatives with 2-(phenylethynyl)anilines 212 and oxabe...
Scheme 39: Rh-catalyzed domino carborhodation of heterobicyclic alkenes 30 with B2pin2 (53).
Scheme 40: Rh-catalyzed three-component 1,2-carboamidation reaction of bicyclic alkenes 30 with aromatic and h...
Scheme 41: Pd-catalyzed diarylation and dialkenylation reactions of norbornene derivatives.
Scheme 42: Three-component Pd-catalyzed arylalkynylation reactions of bicyclic alkenes.
Scheme 43: Three-component Pd-catalyzed arylalkynylation reactions of norbornene and DFT mechanistic study.
Scheme 44: Pd-catalyzed three-component coupling N-tosylhydrazones 236, aryl halides 66, and norbornene (15a).
Scheme 45: Pd-catalyzed arylboration and allylboration of bicyclic alkenes.
Scheme 46: Pd-catalyzed, three-component annulation of aryl iodides 66, alkenyl bromides 241, and bicyclic alk...
Scheme 47: Pd-catalyzed double insertion/annulation reaction for synthesizing tetrasubstituted olefins.
Scheme 48: Pd-catalyzed aminocyclopropanation of bicyclic alkenes 1 with 5-iodopent-4-enylamine derivatives 249...
Scheme 49: Pd-catalyzed, three-component coupling of alkynyl bromides 62 and norbornene derivatives 15 with el...
Scheme 50: Pd-catalyzed intramolecular cyclization/ring-opening reaction of heterobicyclic alkenes 30 with 2-i...
Scheme 51: Pd-catalyzed dimer- and trimerization of oxabenzonorbornadiene derivatives 30 with anhydrides 268.
Scheme 52: Pd-catalyzed Catellani-type annulation and retro-DielsāAlder of norbornadiene 15b yielding fused xa...
Scheme 53: Pd-catalyzed hydroarylation and heteroannulation of urea-derived bicyclic alkenes 158 and aryl iodi...
Scheme 54: Access to fused 8-membered sulfoximine heterocycles 284/285 via Pd-catalyzed Catellani annulation c...
Scheme 55: Pd-catalyzed 2,2-bifunctionalization of bicyclic alkenes 1 generating spirobicyclic xanthone deriva...
Scheme 56: Pd-catalyzed Catellani-type annulation and retro-DielsāAlder of norbornadiene (15b) producing subst...
Scheme 57: Pd-catalyzed [2 + 2 + 1] annulation furnishing bicyclic-fused indanes 281 and 283.
Scheme 58: Pd-catalyzed ring-opening/ring-closing cascade of diazabicyclic alkenes 130a.
Scheme 59: Pd-NHC-catalyzed cyclopentannulation of diazabicyclic alkenes 130a.
Scheme 60: Pd-catalyzed annulation cascade generating diazabicyclic-fused indanones 292 and indanols 294.
Scheme 61: Pd-catalyzed skeletal rearrangement of spirotricyclic alkenes 176 towards large polycyclic benzofur...
Scheme 62: Pd-catalyzed oxidative annulation of aromatic enamides 298 and diazabicyclic alkenes 130a.
Scheme 63: Accessing 3,4,5-trisubstituted cyclopentenes 300, 301, 302 via the Pd-catalyzed domino reaction of ...
Scheme 64: Palladacycle-catalyzed ring-expansion/cyclization domino reactions of terminal alkynes and bicyclic...
Scheme 65: Pd-catalyzed carboesterification of norbornene (15a) with alkynes, furnishing α-methylene γ-lactone...
Beilstein J. Org. Chem. 2023, 19, 448ā473, doi:10.3762/bjoc.19.35
Graphical Abstract
Scheme 1: Transition-metal-catalyzed CāXRF bond formation by CāH bond activation: an overview.
Scheme 2: Cu(OAc)2-promoted mono- and ditrifluoromethylthiolation of benzamide derivatives derived from 8-ami...
Scheme 3: Trifluoromethylthiolation of azacalix[1]arene[3]pyridines using copper salts and a nucleophilic SCF3...
Scheme 4: Working hypothesis for the palladium-catalyzed CāH trifluoromethylthiolation reaction.
Scheme 5: Trifluoromethylthiolation of 2-arylpyridine derivatives and analogs by means of palladium-catalyzed...
Scheme 6: C(sp2)āSCF3 bond formation by Pd-catalyzed CāH bond activation using AgSCF3 and SelectfluorĀ® as rep...
Scheme 7: Palladium-catalyzed ortho-trifluoromethylthiolation of 2-arylpyridine derivatives reported by the g...
Scheme 8: Palladium-catalyzed ortho-trifluoromethylthiolation of 2-arylpyridine and analogs reported by Anbar...
Scheme 9: Mono- and ditrifluoromethylthiolation of benzamide derivatives derived from 8-aminoquinoline using ...
Scheme 10: Regioselective Cp*Rh(III)-catalyzed directed trifluoromethylthiolation reported by the group of Li [123]...
Scheme 11: Cp*Co(III)-catalyzed ortho-trifluoromethylthiolation of 2-phenylpyridine and 2-phenylpyrimidine der...
Scheme 12: Cp*Co(III)-catalyzed ortho-trifluoromethylthiolation of 2-phenylpyridine and 6-phenylpurine derivat...
Scheme 13: Diastereoselective trifluoromethylthiolation of acrylamide derivatives derived from 8-aminoquinolin...
Scheme 14: C(sp3)āSCF3 bond formation on aliphatic amide derivatives derived from 8-aminoquinoline by palladiu...
Scheme 15: Regio- and diastereoselective difluoromethylthiolation of acrylamides under palladium catalysis rep...
Scheme 16: Palladium-catalyzed (ethoxycarbonyl)difluoromethylthiolation reaction of 2-(hetero)aryl and 2-(α-ar...
Scheme 17: Pd(II)-catalyzed trifluoromethylselenolation of benzamides derived from 5-methoxy-8-aminoquinoline ...
Scheme 18: Pd(II)-catalyzed trifluoromethylselenolation of acrylamide derivatives derived from 5-methoxy-8-ami...
Scheme 19: Transition-metal-catalyzed dehydrogenative 2,2,2-trifluoroethoxylation of (hetero)aromatic derivati...
Scheme 20: Pd(II)-catalyzed ortho-2,2,2-trifluoroethoxylation of N-sulfonylbenzamides reported by the group of...
Scheme 21: Pd(II)-catalyzed selective 2,2,2-trifluoroethoxylation and other fluoroalkoxylations of naphthalene...
Scheme 22: Pd(II)-catalyzed selective ortho-2,2,2-trifluoroethoxylation of benzaldehyde derivatives by means o...
Scheme 23: Pd(II)-catalyzed selective ortho-2,2,2-trifluoroethoxylation (and other fluoroalkoxylations) of ben...
Scheme 24: Pd(II)-catalyzed selective 2,2,2-trifluoroethoxylation of aliphatic amides using a bidentate direct...
Beilstein J. Org. Chem. 2023, 19, 325ā348, doi:10.3762/bjoc.19.28
Graphical Abstract
Scheme 1: Group 13 exchange.
Scheme 2: Borane-catalysed hydroboration of alkynes and the proposed mechanism.
Scheme 3: a) Borane-catalysed hydroboration of alkenes and the proposed mechanism. b) H-B-9-BBN-catalysed dou...
Scheme 4: a) Amine-borane-catalysed CāH borylation of heterocycles and the proposed mechanism. b) Benzoic aci...
Scheme 5: Bis(pentafluorophenyl)borane-catalysed dimerisation of allenes and the proposed mechanism.
Scheme 6: Alkoxide-promoted hydroboration of heterocycles and the proposed mechanism.
Scheme 7: Borane-catalysed reduction of indoles and the proposed mechanism.
Scheme 8: H-B-9-BBN-catalysed hydrocyanation of enones and the proposed mechanism.
Scheme 9: Borane-catalysed hydroboration of nitriles and the proposed mechanism.
Scheme 10: Myrtanylborane-catalysed asymmetric reduction of propargylic ketones and the proposed mechanism.
Scheme 11: H-B-9-BBN-catalysed CāF esterification of alkyl fluorides and the proposed mechanism.
Scheme 12: H-B-9-BBN-catalysed 1,4-hydroboration of enones and the proposed mechanism.
Scheme 13: Boric acid-promoted reduction of esters, lactones, and carbonates and the proposed mechanism.
Scheme 14: H-B-9-BBN-catalysed reductive aldol-type reaction and the proposed mechanism.
Scheme 15: H-B-9-BBN-catalysed diastereoselective allylation of ketones and the Ph-BBD-catalysed enantioselect...
Scheme 16: H-B-9-BBN-catalysed CāF arylation of benzyl fluorides and the proposed mechanism.
Scheme 17: Borane-catalysed SāH borylation of thiols and the proposed mechanism.
Scheme 18: Borane-catalysed hydroalumination of alkenes and allenes.
Scheme 19: a) Aluminium-catalysed hydroboration of alkynes and example catalysts. b) Deprotonation mechanistic...
Scheme 20: Aluminium-catalysed hydroboration of alkenes and the proposed mechanism.
Scheme 21: Aluminium-catalysed CāH borylation of terminal alkynes and the proposed mechanism.
Scheme 22: Aluminium-catalysed dehydrocoupling of amines, alcohols, and thiols with H-B-9-BBN or HBpin and the...
Scheme 23: Aluminium-catalysed hydroboration of unsaturated compounds and the general reaction mechanism.
Scheme 24: a) Gallium-catalysed asymmetric hydroboration of ketones and the proposed mechanism. b) Gallium-cat...
Scheme 25: Gallium(I)-catalysed allylation/propargylation of acetals and aminals and the proposed mechanism.
Scheme 26: Indium(I)-catalysed allylation/propargylation of acetals, aminals, and alkyl ethers.
Scheme 27: Ironāindium cocatalysed double hydroboration of nitriles and the proposed mechanism.
Figure 1: a) The number of reports for a given group 13 exchange in catalysis. b) Average free energy barrier...
Beilstein J. Org. Chem. 2023, 19, 245ā281, doi:10.3762/bjoc.19.23
Graphical Abstract
Figure 1: Examples of terpenes containing a bicyclo[3.6.0]undecane motif.
Figure 2: Commercially available first and second generation Grubbs and HoveydaāGrubbs catalysts.
Figure 3: Examples of strategies to access the fusicoccan and ophiobolin tricyclic core structure by RCM.
Scheme 1: Synthesis of bicyclic core structure 12 of ophiobolin M (13) and cycloaraneosene (14).
Scheme 2: Synthesis of the core structure 21 of ophiobolins and fusicoccanes.
Scheme 3: Ring-closing metathesis attempts starting from thioester 22.
Scheme 4: Total synthesis of ent-fusicoauritone (28).
Figure 4: General structure of ophiobolins and congeners.
Scheme 5: Total synthesis of (+)-ophiobolin A (8).
Scheme 6: Investigation of RCM for the synthesis of ophiobolin A (8). Path A) RCM with TBDPS-protected alcoho...
Scheme 7: Synthesis of the core structure of cotylenin A aglycon, cotylenol (50).
Scheme 8: Synthesis of tricyclic core structure of fusicoccans.
Scheme 9: Total synthesis of (ā)-teubrevin G (59).
Scheme 10: Synthesis of the core skeleton 63 of the basmane family.
Scheme 11: Total synthesis of (±)-schindilactone A (68).
Scheme 12: Total synthesis of dactylol (72).
Scheme 13: Ring-closing metathesis for the total synthesis of (±)-asteriscanolide (2).
Scheme 14: Synthesis of the simplified skeleton of pleuromutilin (1).
Scheme 15: Total synthesis of (ā)-nitidasin (93) using a ring-closing metathesis to construct the eight-member...
Scheme 16: Total synthesis of (±)-naupliolide (97).
Scheme 17: Synthesis of the A-B ring structure of fusicoccane (101).
Scheme 18: First attempts of TRCM of dienyne substrates.
Scheme 19: TRCM on optimized substrates towards the synthesis of ophiobolin A (8).
Scheme 20: Tandem ring-closing metathesis for the synthesis of variecolin intermediates 114 and 115.
Scheme 21: Synthesis of poitediol (118) using the allylsilane ring-closing metathesis.
Scheme 22: Access to scaffold 122 by a NHK coupling reaction.
Scheme 23: Key step to construct the [5-8] bicyclooctanone core of aquatolide (4).
Scheme 24: Initial strategy to access aquatolide (4).
Scheme 25: Synthetic plan to cotylenin A (130).
Scheme 26: [5-8] Bicyclic structure of brachialactone (7) constructed by a MizorokiāHeck reaction.
Scheme 27: Influence of the replacement of the allylic alcohol moiety.
Scheme 28: Formation of variecolin intermediate 140 through a SmI2-mediated Barbier-type reaction.
Scheme 29: SmI2-mediated ketyl addition. Pleuromutilin (1) eight-membered ring closure via C5āC14 bond formati...
Scheme 30: SmI2-mediated dialdehyde cyclization cascade of [5-8-6] pleuromutilin scaffold 149.
Scheme 31: A) Modular synthetic route to mutilin and pleuromutilin family members by Herzonās group. B) Scaffo...
Scheme 32: Photocatalyzed oxidative ring expansion in pleuromutilin (1) total synthesis.
Scheme 33: Reductive radical cascade cyclization route towards (ā)-6-epi-ophiobolin N (168).
Scheme 34: Reductive radical cascade cyclization route towards (+)-6-epi-ophiobolin A (173).
Scheme 35: Radical 8-endo-trig-cyclization of a xanthate precursor.
Figure 5: Structural representations of hypoestin A (177), albolic acid (178), and ceroplastol II (179) beari...
Scheme 36: Synthesis of the common [5-8-5] tricyclic intermediate of hypoestin A (177), albolic acid (178), an...
Scheme 37: Asymmetric synthesis of hypoestin A (177), albolic acid (178), and ceroplastol II (179).
Figure 6: Scope of the PausonāKhand reaction.
Scheme 38: Nazarov cyclization revealing the fusicoauritone core structure 192.
Scheme 39: Synthesis of fusicoauritone (28) through Nazarov cyclization.
Scheme 40: (+)-Epoxydictymene (5) synthesis through a Nicholas cyclization followed by a PausonāKhand reaction...
Scheme 41: Synthesis of aquatolide (4) by a Mukaiyama-type aldolisation.
Scheme 42: Tandem Wolff/Cope rearrangement furnishing the A-B bicyclic moiety 204 of variecolin.
Scheme 43: Asymmetric synthesis of the A-B bicyclic core 205 and 206 of variecolin.
Scheme 44: Formation of [5-8]-fused rings by cyclization under thermal activation.
Scheme 45: Construction of the [5-8-6] tricyclic core structure of variecolin (3) by DielsāAlder reaction.
Scheme 46: Synthesis of the [6-4-8-5]-tetracyclic skeleton by palladium-mediated cyclization.
Scheme 47: Access to the [5-8] bicyclic core structure of asteriscanolide (227) through rhodium-catalyzed cycl...
Scheme 48: Total syntheses of asterisca-3(15),6-diene (230) and asteriscanolide (2) with a Rh-catalyzed cycliz...
Scheme 49: Photocyclization of 2-pyridones to access the [5-8-5] backbone of fusicoccanes.
Scheme 50: Total synthesis of (+)-asteriscunolide D (245) and (+)-aquatolide (4) through photocyclization.
Scheme 51: Biocatalysis pathway to construct the [5-8-5] tricyclic scaffold of brassicicenes.
Scheme 52: Influence of the CotB2 mutant over the cyclizationās outcome of GGDP.
Beilstein J. Org. Chem. 2023, 19, 158ā166, doi:10.3762/bjoc.19.15
Scheme 1: Structure of the (8E,10Z)-tetradecadienal (1, sex pheromone of the horse-chestnut leaf miner) and r...
Scheme 2: a) Alkylāvinyl seminal cross-coupling reaction by Kochi; b) improved procedure described by Cahiez.
Scheme 3: Iron-catalyzed cross-coupling of n-OctMgCl with a 1-butadienyl phosphate.
Scheme 4: Synthesis of several insect sex pheromones (a) red bollworm moth, b) European grapevine moth, c) ho...
Scheme 5: Cross-coupling of alkyl Grignard reagents with a) alkenyl or b) aryl halides involving EtOMgCl as a...
Scheme 6: Total synthesis of codling moth sex pheromone 4 using an iron-mediated cross-coupling between an α,...
Beilstein J. Org. Chem. 2022, 18, 1532ā1538, doi:10.3762/bjoc.18.162
Graphical Abstract
Figure 1: Selected examples of biologically active natural products bearing a spirofuranoxindole moiety.
Scheme 1: Synthesis of spiro[dihydrofuran-2,3'-oxindoles] from enones and diazooxindoles.
Scheme 2: Cycloaddition reactions of [e]-fused 1H-pyrrole-2,3-diones.
Scheme 3: The model reaction of FPD 1a and diazooxindole 2a.
Scheme 4: The reaction of FPD 1k with diazooxindole 2a.
Scheme 5: A) Plausible mechanism of formal [4 + 1] cycloaddition of FPDs 1 with diazooxindoles 2 (negative ch...
Beilstein J. Org. Chem. 2022, 18, 1518ā1523, doi:10.3762/bjoc.18.160
Graphical Abstract
Scheme 1: Scheme showing the transformation of the Br-substrates to phosphonate esters and then to phosphonic...
Figure 1: Experimental setup for the improved CāP cross-coupling reaction.
Beilstein J. Org. Chem. 2022, 18, 1505ā1506, doi:10.3762/bjoc.18.158
Beilstein J. Org. Chem. 2022, 18, 1424ā1434, doi:10.3762/bjoc.18.148
Graphical Abstract
Figure 1: Adamantane-based tripodal scaffolds and current work.
Scheme 1: A general strategy for the assembly of TAAD derivatives.
Scheme 2: Synthesis of acyclic precursors to 3N-TAADs, 2N,1O-TAADs, and 1N,2O-TAADs.
Scheme 3: Synthesis of 3N-TAADs, 2N,1O-TAADs, and 1N,2O-TAADs. *Yield based on compound 14.
Scheme 4: Deprotection of TAAD 8b and subsequent complexation with phenylboronic acid.
Scheme 5: Quaternization of TAADs 4c, 4e, 6a, and 8a followed by deprotection of N-Boc groups.
Figure 2: General view of the 1,4,6,10-tetraazaadamantane motif in X-ray structures of the obtained N-TAAD de...
Figure 3: (a) General structure of hostāguest complexes of 3N-TAADs with water. (b) The general structure of ...
Figure 4: (a) Dynamic processes in TAADs 4 and complexation with ROH. (b) Fragment of 1H NMR spectra of Bn-4c...
Beilstein J. Org. Chem. 2022, 18, 1332ā1337, doi:10.3762/bjoc.18.138
Graphical Abstract
Scheme 1: a) Derivatives of primary amines in materials chemistry, pharmaceuticals, and agrochemicals; b) thi...
Scheme 2: Substrate scope of borane-catalysed nitrile hydroboration with HBpin. Conditions: nitrile (0.50 mmo...
Scheme 3: a) Proposed mechanism; b) H-B-9-BBN-catalysed heptanenitrile hydroboration (yield determined by 1H ...
Beilstein J. Org. Chem. 2022, 18, 688ā706, doi:10.3762/bjoc.18.70
Graphical Abstract
Figure 1: Inductive heating, a powerful tool in industry and the Life Sciences.
Figure 2: Electric displacement field of a ferromagnetic and superparamagnetic material.
Figure 3: Temperature profiles of reactors heated conventionally and by RF heating (Figure 3 redrawn from [24]).
Scheme 1: Continuous flow synthesis of isopulegol (2) from citronellal (1).
Scheme 2: Dry (reaction 1) and steam (reaction 2) methane reforming.
Scheme 3: Calcination and RF heating.
Scheme 4: The continuously operated āSabatierā process.
Scheme 5: Biofuel production from biomass using inductive heating for pyrolysis.
Scheme 6: Water electrolysis using an inductively heated electrolysis cell.
Scheme 7: Dimroth rearrangement (reaction 1) and three-component reaction (reaction 2) to propargyl amines 8 ...
Figure 4: A. Flow reactor filled with magnetic nanostructured particles (MagSilicaTM) and packed bed reactor ...
Scheme 8: Claisen rearrangement in flow: A. comparison between conventional heating (external oil bath), micr...
Scheme 9: Continuous flow reactions and comparison with batch reaction (oil bath). A. Pd-catalyzed transfer h...
Scheme 10: Continuous flow reactions and comparison with batch reaction (oil bath). A. pericyclic reactions an...
Scheme 11: Reactions under flow conditions using inductively heated fixed-bed materials serving as stoichiomet...
Scheme 12: Reactions under flow conditions using inductively heated fixed-bed materials serving as catalysts: ...
Scheme 13: Two step flow protocol for the preparation of 1,1'-diarylalkanes 77 from ketones and aldehydes 74, ...
Scheme 14: O-Alkylation, the last step in the multistep flow synthesis of Iloperidone (80) accompanied with a ...
Scheme 15: Continuous two-step flow process consisting of Grignard reaction followed by water elimination bein...
Scheme 16: Inductively heated continuous flow protocol for the synthesis of Iso E Super (88) [91,92].
Scheme 17: Three-step continuous flow synthesis of macrocycles 89 and 90 with musk-like olfactoric properties.
Beilstein J. Org. Chem. 2022, 18, 381ā419, doi:10.3762/bjoc.18.43
Graphical Abstract
Figure 1: Natural bioactive naphthoquinones.
Figure 2: Chemical structures of vitamins K.
Figure 3: Redox cycle of menadione.
Scheme 1: Selected approaches for menadione synthesis using silver(I) as a catalyst.
Scheme 2: Methylation approaches for the preparation of menadione from 1,4-naphthoquinone using tert-butyl hy...
Scheme 3: Methylation approach of 1,4-naphthoquinone using i) rhodium complexes/methylboronic acid and ii) bi...
Scheme 4: Synthesis of menadione (10) from itaconic acid.
Scheme 5: Menadione synthesis via DielsāAlder reaction.
Scheme 6: Synthesis of menadione (10) using p-cresol as a synthetic precursor.
Scheme 7: Synthesis of menadione (10) via demethoxycarbonylating annulation of methyl methacrylate.
Scheme 8: Furan 34 used as a diene in a DielsāAlder reaction for the synthesis of menadione (10).
Scheme 9: o-Toluidine as a dienophile in a DielsāAlder reaction for the synthesis of menadione (10).
Scheme 10: Representation of electrochemical synthesis of menadione.
Figure 4: Reaction sites and reaction types of menadione as substrate.
Scheme 11: DBU-catalyzed epoxidation of menadione (10).
Scheme 12: Phase-transfer catalysis for the epoxidation of menadione.
Scheme 13: Menadione epoxidation using a hydroperoxide derived from (+)-norcamphor.
Scheme 14: Enantioselective DielsāAlder reaction for the synthesis of asymmetric quinone 50 catalyzed by a chi...
Scheme 15: Optimized reaction conditions for the synthesis of anthra[9,1-bc]pyranone.
Scheme 16: Synthesis of anthra[9,1-bc]furanone, anthra[9,1-bc]pyridine, and anthra[9,1-bc]pyrrole derivatives.
Scheme 17: Synthesis of derivatives employing protected trienes.
Scheme 18: Synthesis of cyclobutene derivatives of menadione.
Scheme 19: Menadione reduction reactions using sodium hydrosulfite.
Scheme 20: Green methodology for menadiol synthesis and pegylation.
Scheme 21: Menadione reduction by 5,6-O-isopropylidene-Ź-ascorbic acid under UV light irradiation.
Scheme 22: Selected approaches of menadione hydroacetylation to diacetylated menadiol.
Scheme 23: ThieleāWinter reaction catalyzed by Bi(OTf)3.
Scheme 24: Carbonyl condensation of menadione using resorcinol and a hydrazone derivative.
Scheme 25: Condensation reaction of menadione with thiosemicarbazide.
Scheme 26: Condensation reaction of menadione with acylhydrazides.
Scheme 27: Menadione derivatives functionalized with organochalcogens.
Scheme 28: Synthesis of selenium-menadione conjugates derived from chloromethylated menadione 84.
Scheme 29: Menadione alkylation by the KochiāAnderson method.
Scheme 30: Menadione alkylation by diacids.
Scheme 31: Menadione alkylation by heterocycles-substituted carboxylic acids.
Scheme 32: Menadione alkylation by bromoalkyl-substituted carboxylic acids.
Scheme 33: Menadione alkylation by complex carboxylic acids.
Scheme 34: KochiāAnderson method variations for the menadione alkylation via oxidative decarboxylation of carb...
Scheme 35: Copper-catalyzed menadione alkylation via free radicals.
Scheme 36: Nickel-catalyzed menadione cyanoalkylation.
Scheme 37: Iron-catalyzed alkylation of menadione.
Scheme 38: Selected approaches to menadione alkylation.
Scheme 39: Menadione acylation by photo-FriedelāCrafts acylation reported by Waske and co-workers.
Scheme 40: Menadione acylation by Westwood procedure.
Scheme 41: Synthesis of 3-benzoylmenadione via metal-free TBAI/TBHP system.
Scheme 42: Michael-type addition of amines to menadione reported by Kallmayer.
Scheme 43: Synthesis of amino-menadione derivatives using polyalkylamines.
Scheme 44: Selected examples for the synthesis of different amino-substituted menadione derivatives.
Scheme 45: Selected examples of Michael-type addition of complex amines to menadione (10).
Scheme 46: Addition of different natural α-amino acids to menadione.
Scheme 47: Michael-type addition of amines to menadione using silica-supported perchloric acid.
Scheme 48: Indolylnaphthoquinone or indolylnaphthalene-1,4-diol synthesis reported by Yadav et al.
Scheme 49: Indolylnaphthoquinone synthesis reported by Tanoue and co-workers.
Scheme 50: Indolylnaphthoquinone synthesis from menadione by Escobeto-GonzƔlez and co-workers.
Scheme 51: Synthesis of menadione analogues functionalized with thiols.
Scheme 52: Synthesis of menadione-derived symmetrical derivatives through reaction with dithiols.
Scheme 53: Mercaptoalkyl acids as nucleophiles in Michael-type addition reaction to menadione.
Scheme 54: Reactions of menadione (10) with cysteine derivatives for the synthesis of quinoproteins.
Scheme 55: Synthesis of menadione-glutathione conjugate 152 by Michael-type addition.
Beilstein J. Org. Chem. 2022, 18, 86ā88, doi:10.3762/bjoc.18.8
Beilstein J. Org. Chem. 2021, 17, 2848ā2893, doi:10.3762/bjoc.17.196
Graphical Abstract
Figure 1: Price comparison among iron and other transition metals used in catalysis.
Scheme 1: Typical modes of CāC bond formation.
Scheme 2: The components of an iron-catalyzed domino reaction.
Scheme 3: Iron-catalyzed tandem cyclization and cross-coupling reactions of iodoalkanes 1 with aryl Grignard ...
Scheme 4: Three component iron-catalyzed dicarbofunctionalization of vinyl cyclopropanes 14.
Scheme 5: Three-component iron-catalyzed dicarbofunctionalization of alkenes 21.
Scheme 6: Double carbomagnesiation of internal alkynes 31 with alkyl Grignard reagents 32.
Scheme 7: Iron-catalyzed cycloisomerization/cross-coupling of enyne derivatives 35 with alkyl Grignard reagen...
Scheme 8: Iron-catalyzed spirocyclization/cross-coupling cascade.
Scheme 9: Iron-catalyzed alkenylboration of alkenes 50.
Scheme 10: N-AlkylāN-aryl acrylamide 60 CDC cyclization with C(sp3)āH bonds adjacent to a heteroatom.
Scheme 11: 1,2-Carboacylation of activated alkenes 60 with aldehydes 65 and alcohols 67.
Scheme 12: Iron-catalyzed dicarbonylation of activated alkenes 68 with alcohols 67.
Scheme 13: Iron-catalyzed cyanoalkylation/radical dearomatization of acrylamides 75.
Scheme 14: Synergistic photoredox/iron-catalyzed 1,2-dialkylation of alkenes 82 with common alkanes 83 and 1,3...
Scheme 15: Iron-catalyzed oxidative coupling/cyclization of phenol derivatives 86 and alkenes 87.
Scheme 16: Iron-catalyzed carbosulfonylation of activated alkenes 60.
Scheme 17: Iron-catalyzed oxidative spirocyclization of N-arylpropiolamides 91 with silanes 92 and tert-butyl ...
Scheme 18: Iron-catalyzed free radical cascade difunctionalization of unsaturated benzamides 94 with silanes 92...
Scheme 19: Iron-catalyzed cyclization of olefinic dicarbonyl compounds 97 and 100 with C(sp3)āH bonds.
Scheme 20: Radical difunctionalization of o-vinylanilides 102 with ketones and esters 103.
Scheme 21: Dehydrogenative 1,2-carboamination of alkenes 82 with alkyl nitriles 76 and amines 105.
Scheme 22: Iron-catalyzed intermolecular 1,2-difunctionalization of conjugated alkenes 107 with silanes 92 and...
Scheme 23: Four-component radical difunctionalization of chemically distinct alkenes 114/115 with aldehydes 65...
Scheme 24: Iron-catalyzed carbocarbonylation of activated alkenes 60 with carbazates 117.
Scheme 25: Iron-catalyzed radical 6-endo cyclization of dienes 119 with carbazates 117.
Scheme 26: Iron-catalyzed decarboxylative synthesis of functionalized oxindoles 130 with tert-butyl peresters ...
Scheme 27: Ironācatalyzed decarboxylative alkylation/cyclization of cinnamamides 131/134.
Scheme 28: Iron-catalyzed carbochloromethylation of activated alkenes 60.
Scheme 29: Iron-catalyzed trifluoromethylation of dienes 142.
Scheme 30: Iron-catalyzed, silver-mediated arylalkylation of conjugated alkenes 115.
Scheme 31: Iron-catalyzed three-component carboazidation of conjugated alkenes 115 with alkanes 101/139b and t...
Scheme 32: Iron-catalyzed carboazidation of alkenes 82 and alkynes 160 with iodoalkanes 20 and trimethylsilyl ...
Scheme 33: Iron-catalyzed asymmetric carboazidation of styrene derivatives 115.
Scheme 34: Iron-catalyzed carboamination of conjugated alkenes 115 with alkyl diacyl peroxides 163 and acetoni...
Scheme 35: Iron-catalyzed carboamination using oxime esters 165 and arenes 166.
Scheme 36: Iron-catalyzed iminyl radical-triggered [5 + 2] and [5 + 1] annulation reactions with oxime esters ...
Scheme 37: Iron-catalyzed decarboxylative alkyl etherification of alkenes 108 with alcohols 67 and aliphatic a...
Scheme 38: Iron-catalyzed inter-/intramolecular alkylative cyclization of carboxylic acid and alcohol-tethered...
Scheme 39: Iron-catalyzed intermolecular trifluoromethyl-acyloxylation of styrene derivatives 115.
Scheme 40: Iron-catalyzed carboiodination of terminal alkenes and alkynes 180.
Scheme 41: Copper/iron-cocatalyzed cascade perfluoroalkylation/cyclization of 1,6-enynes 183/185.
Scheme 42: Iron-catalyzed stereoselective carbosilylation of internal alkynes 187.
Scheme 43: Synergistic photoredox/iron catalyzed difluoroalkylationāthiolation of alkenes 82.
Scheme 44: Iron-catalyzed three-component aminoazidation of alkenes 82.
Scheme 45: Iron-catalyzed intra-/intermolecular aminoazidation of alkenes 194.
Scheme 46: Stereoselective iron-catalyzed oxyazidation of enamides 196 using hypervalent iodine reagents 197.
Scheme 47: Iron-catalyzed aminooxygenation for the synthesis of unprotected amino alcohols 200.
Scheme 48: Iron-catalyzed intramolecular aminofluorination of alkenes 209.
Scheme 49: Iron-catalyzed intramolecular aminochlorination and aminobromination of alkenes 209.
Scheme 50: Iron-catalyzed intermolecular aminofluorination of alkenes 82.
Scheme 51: Iron-catalyzed aminochlorination of alkenes 82.
Scheme 52: Iron-catalyzed phosphinoylazidation of alkenes 108.
Scheme 53: Synergistic photoredox/iron-catalyzed three-component aminoselenation of trisubstituted alkenes 82.
Beilstein J. Org. Chem. 2021, 17, 2729ā2764, doi:10.3762/bjoc.17.185
Graphical Abstract
Figure 1: Representative examples of axially chiral biaryls, heterobiaryls, spiranes and allenes as ligands a...
Figure 2: Selected examples of axially chiral drugs and bioactive molecules.
Figure 3: Axially chiral functional materials and supramolecules.
Figure 4: Important chiral phosphoric acid scaffolds used in this review.
Scheme 1: Atroposelective arylāaryl-bond formation by employing a facile [3,3]-sigmatropic rearrangement.
Scheme 2: Atroposelective synthesis of axially chiral biaryl amino alcohols 5.
Scheme 3: The enantioselective reaction of quinone and 2-naphthol derivatives.
Scheme 4: Enantioselective synthesis of multisubstituted biaryls.
Scheme 5: Enantioselective synthesis of axially chiral quinoline-derived biaryl atropisomers mediated by chir...
Scheme 6: Pd-Catalyzed atroposelective CāH olefination of biarylamines.
Scheme 7: Palladium-catalyzed directed atroposelective CāH allylation.
Scheme 8: Enantioselective synthesis of axially chiral (a) aryl indoles and (b) biaryldiols.
Scheme 9: Asymmetric arylation of indoles enabled by azo groups.
Scheme 10: Proposed mechanism for the asymmetric arylation of indoles.
Scheme 11: Enantioselective synthesis of axially chiral N-arylindoles [38].
Scheme 12: Enantioselective [3 + 2] formal cycloaddition and central-to-axial chirality conversion.
Scheme 13: Organocatalytic atroposelective arene functionalization of nitrosonaphthalene with indoles.
Scheme 14: Proposed reaction mechanism for the atroposelective arene functionalization of nitrosonaphthalenes.
Scheme 15: Asymmetric construction of axially chiral naphthylindoles [65].
Scheme 16: Enantioselective synthesis of axially chiral 3,3ā-bisindoles [66].
Scheme 17: Atroposelective synthesis of 3,3ā-bisiindoles bearing axial and central chirality.
Scheme 18: Enantioselective synthesis of axially chiral 3,3ā-bisindoles bearing single axial chirality.
Scheme 19: Enantioselective reaction of azonaphthalenes with various pyrazolones.
Scheme 20: Enantioselective and atroposelective synthesis of axially chiral N-arylcarbazoles [73].
Scheme 21: Atroposelective cyclodehydration reaction.
Scheme 22: Atroposelective construction of axially chiral N-arylbenzimidazoles [78].
Scheme 23: Proposed reaction mechanism for the atroposelective synthesis of axially chiral N-arylbenzimidazole...
Scheme 24: Atroposelective synthesis of axially chiral arylpyrroles [21].
Scheme 25: Synthesis of axially chiral arylquinazolinones and its reaction pathway [35].
Scheme 26: Synthesis of axially chiral aryquinoline by FriedlaĢnder heteroannulation reaction and its proposed...
Scheme 27: Povarov cycloadditionāoxidative chirality conversion process.
Scheme 28: Atroposelective synthesis of oxindole-based axially chiral styrenes via kinetic resolution.
Scheme 29: Synthesis of axially chiral alkene-indole frame works [45].
Scheme 30: Proposed reaction mechanism for axially chiral alkene-indoles.
Scheme 31: Atroposelective CāH aminations of N-aryl-2-naphthylamines with azodicarboxylates.
Scheme 32: Synthesis of brominated atropisomeric N-arylquinoids.
Scheme 33: The enantioselective syntheses of axially chiral SPINOL derivatives.
Scheme 34: γ-Addition reaction of various 2,3-disubstituted indoles to β,γ-alkynyl-α-imino esters.
Scheme 35: Regio- and stereoselective γ-addition reactions of isoxazol-5(4H)-ones to β,γ-alkynyl-α-imino ester...
Scheme 36: Synthesis of chiral tetrasubstituted allenes and naphthopyrans.
Scheme 37: Asymmetric remote 1,8-conjugate additions of thiazolones and azlactones to propargyl alcohols.
Scheme 38: Synthesis of chiral allenes from 1-substituted 2-naphthols [107].
Beilstein J. Org. Chem. 2021, 17, 2315ā2320, doi:10.3762/bjoc.17.149
Graphical Abstract
Scheme 1: Reaction scope. Conditions: quinone 1 (0.3 mmol), aniline 4 (1.2 mmol), HBF4 (1.5 mmol), t-BuONO (1...
Scheme 2: Synthesis of betulinan A and its analog 5b. Conditions: quinone 3 (0.1 mmol), NaOMe (0.25 mmol) in ...
Beilstein J. Org. Chem. 2021, 17, 2209ā2259, doi:10.3762/bjoc.17.143
Graphical Abstract
Scheme 1: Nickel-catalyzed cross-coupling versus CāH activation.
Figure 1: Oxidative and reductive quenching cycles of a photocatalyst. [PC] = photocatalyst, A = acceptor, D ...
Scheme 2: Photoredox nickel-catalyzed C(sp3)āH arylation of dimethylaniline (1a).
Scheme 3: Photoredox nickel-catalyzed arylation of α-amino, α-oxy and benzylic C(sp3)āH bonds with aryl bromi...
Figure 2: Proposed catalytic cycle for the photoredox-mediated HAT and nickel catalysis enabled C(sp3)āH aryl...
Scheme 4: Photoredox arylation of α-amino C(sp3)āH bonds with aryl iodides.
Figure 3: Proposed mechanism for photoredox nickel-catalyzed α-amino CāH arylation with aryl iodides.
Scheme 5: Nickel-catalyzed α-oxy C(sp3)āH arylation of cyclic and acyclic ethers.
Figure 4: Proposed catalytic cycle for the C(sp3)āH arylation of cyclic and acyclic ethers.
Scheme 6: Photochemical nickel-catalyzed CāH arylation of ethers.
Figure 5: Proposed catalytic cycle for the nickel-catalyzed arylation of ethers with aryl bromides.
Scheme 7: Nickel-catalyzed α-amino C(sp3)āH arylation with aryl tosylates.
Scheme 8: Arylation of α-amino C(sp3)āH bonds by in situ generated aryl tosylates from phenols.
Scheme 9: Formylation of aryl chlorides through redox-neutral 2-functionalization of 1,3-dioxolane (13).
Scheme 10: Photochemical C(sp3)āH arylation via a dual polyoxometalate HAT and nickel catalytic manifold.
Figure 6: Proposed mechanism for C(sp3)āH arylation through dual polyoxometalate HAT and nickel catalytic man...
Scheme 11: Photochemical nickel-catalyzed α-hydroxy CāH arylation.
Scheme 12: Photochemical synthesis of fluoxetine (21).
Scheme 13: Photochemical nickel-catalyzed allylic C(sp3)āH arylation with aryl bromides.
Figure 7: Proposed mechanism for the photochemical nickel-catalyzed allylic C(sp3)āH arylation with aryl brom...
Scheme 14: Photochemical C(sp3)āH arylation by the synergy of ketone HAT catalysis and nickel catalysis.
Figure 8: Proposed mechanism for photochemical C(sp3)āH arylation by the synergy of ketone HAT catalysis and ...
Scheme 15: Benzophenone- and nickel-catalyzed photoredox benzylic CāH arylation.
Scheme 16: Benzaldehyde- and nickel-catalyzed photoredox C(sp3)āH arylation.
Scheme 17: Photoredox and nickel-catalyzed enantioselective benzylic CāH arylation.
Figure 9: Proposed mechanism for the photoredox and nickel-catalyzed enantioselective benzylic CāH arylation.
Scheme 18: Photoredox nickel-catalyzed α-(sp3)āH arylation of secondary benzamides with aryl bromides.
Scheme 19: Enantioselective sp3 α-arylation of benzamides.
Scheme 20: Nickel-catalyzed decarboxylative vinylation/CāH arylation of cyclic oxalates.
Figure 10: Proposed mechanism for the nickel-catalyzed decarboxylative vinylation/CāH arylation of cyclic oxal...
Scheme 21: C(sp3)āH arylation of bioactive molecules using mpg-CN photocatalysis and nickel catalysis.
Figure 11: Proposed mechanism for the mpg-CN/nickel photocatalytic C(sp3)āH arylation.
Scheme 22: Nickel-catalyzed synthesis of 1,1-diarylalkanes from alkyl bromides and aryl bromides.
Figure 12: Proposed mechanism for photoredox nickel-catalyzed C(sp3)āH alkylation via polarity-matched HAT.
Scheme 23: Photoredox nickel-catalyzed C(sp3)āH alkylation via polarity-matched HAT.
Scheme 24: Benzaldehyde- and nickel-catalyzed photoredox C(sp3)āH alkylation of ethers.
Scheme 25: Benzaldehyde- and nickel-catalyzed photoredox C(sp3)āH alkylation of amides and thioethers.
Scheme 26: Photoredox and nickel-catalyzed C(sp3)āH alkylation of benzamides with alkyl bromides.
Scheme 27: CzIPN and nickel-catalyzed C(sp3)āH alkylation of ethers with alkyl bromides.
Figure 13: Proposed mechanism for the CzIPN and nickel-catalyzed C(sp3)āH alkylation of ethers.
Scheme 28: Nickel/photoredox-catalyzed methylation of (hetero)aryl chlorides and acid chlorides using trimethy...
Figure 14: Proposed catalytic cycle for the nickel/photoredox-catalyzed methylation of (hetero)aryl chlorides ...
Scheme 29: Photochemical nickel-catalyzed C(sp3)āH methylations.
Scheme 30: Photoredox nickel catalysis-enabled alkylation of unactivated C(sp3)āH bonds with alkyl bromides.
Scheme 31: Photochemical C(sp3)āH alkenylation with alkenyl tosylates.
Scheme 32: Photoredox nickel-catalyzed hydroalkylation of internal alkynes.
Figure 15: Proposed mechanism for the photoredox nickel-catalyzed hydroalkylation of internal alkynes.
Scheme 33: Photoredox nickel-catalyzed hydroalkylation of activated alkynes with C(sp3)āH bonds.
Scheme 34: Allylation of unactivated C(sp3)āH bonds with allylic chlorides.
Scheme 35: Photochemical nickel-catalyzed α-amino C(sp3)āH allylation of secondary amides with trifluoromethyl...
Scheme 36: Photoredox Ī“ C(sp3)āH allylation of secondary amides with trifluoromethylated alkenes.
Scheme 37: Photoredox nickel-catalyzed acylation of α-amino C(sp3)āH bonds of N-arylamines.
Figure 16: Proposed mechanism for the photoredox nickel-catalyzed acylation of α-amino C(sp3)āH bonds of N-ary...
Scheme 38: Photocatalytic αāacylation of ethers with acid chlorides.
Figure 17: Proposed mechanism for the photocatalytic αāacylation of ethers with acid chlorides.
Scheme 39: Photoredox and nickel-catalyzed C(sp3)āH esterification with chloroformates.
Scheme 40: Photoredox nickel-catalyzed dehydrogenative coupling of benzylic and aldehydic CāH bonds.
Figure 18: Proposed reaction pathway for the photoredox nickel-catalyzed dehydrogenative coupling of benzylic ...
Scheme 41: Photoredox nickel-catalyzed enantioselective acylation of α-amino C(sp3)āH bonds with carboxylic ac...
Scheme 42: Nickel-catalyzed C(sp3)āH acylation with N-acylsuccinimides.
Figure 19: Proposed mechanism for the nickel-catalyzed C(sp3)āH acylation with N-acylsuccinimides.
Scheme 43: Nickel-catalyzed benzylic CāH functionalization with acid chlorides 45.
Scheme 44: Photoredox nickel-catalyzed benzylic CāH acylation with N-acylsuccinimides 84.
Scheme 45: Photoredox nickel-catalyzed acylation of indoles 86 with α-oxoacids 87.
Scheme 46: Nickel-catalyzed aldehyde CāH functionalization.
Figure 20: Proposed catalytic cycle for the photoredox nickel-catalyzed aldehyde CāH functionalization.
Scheme 47: Photoredox carboxylation of methylbenzenes with CO2.
Figure 21: Proposed mechanism for the photoredox carboxylation of methylbenzenes with CO2.
Scheme 48: Decatungstate photo-HAT and nickel catalysis enabled alkene difunctionalization.
Figure 22: Proposed catalytic cycle for the decatungstate photo-HAT and nickel catalysis enabled alkene difunc...
Scheme 49: Diaryl ketone HAT catalysis and nickel catalysis enabled dicarbofunctionalization of alkenes.
Figure 23: Proposed catalytic mechanism for the diaryl ketone HAT catalysis and nickel catalysis enabled dicar...
Scheme 50: Overview of photoredox nickel-catalyzed CāH functionalizations.
Beilstein J. Org. Chem. 2021, 17, 1733ā1751, doi:10.3762/bjoc.17.122
Graphical Abstract
Scheme 1: Mn-catalyzed late-stage fluorination of sclareolide (1) and complex steroid 3.
Figure 1: Proposed reaction mechanism of CāH fluorination by a manganese porphyrin catalyst.
Scheme 2: Late-stage radiofluorination of biologically active complex molecules.
Figure 2: Proposed mechanism of CāH radiofluorination.
Scheme 3: Late-stage CāH azidation of bioactive molecules. a1.5 mol % of Mn(TMP)Cl (5) was used. bMethyl acet...
Figure 3: Proposed reaction mechanism of manganese-catalyzed CāH azidation.
Scheme 4: Mn-catalyzed late-stage CāH azidation of bioactive molecules via electrophotocatalysis. a2.5 mol % ...
Figure 4: Proposed reaction mechanism of electrophotocatalytic azidation.
Scheme 5: Manganaelectro-catalyzed late-stage azidation of bioactive molecules.
Figure 5: Proposed reaction pathway of manganaelectro-catalyzed late-stage CāH azidation.
Scheme 6: Mn-catalyzed late-stage amination of bioactive molecules. a3 Ć MS were used. Protonation with HBF4ā ...
Figure 6: Proposed mechanism of manganese-catalyzed CāH amination.
Scheme 7: Mn-catalyzed CāH methylation of heterocyclic scaffolds commonly found in small-molecule drugs. aDAS...
Scheme 8: Examples of late-stage CāH methylation of bioactive molecules. aDAST activation. bFor insoluble sub...
Scheme 9: A) Mn-catalyzed late-stage CāH alkynylation of peptides. B) Intramolecular late-stage alkynylative ...
Figure 7: Proposed reaction mechanism of Mn(I)-catalyzed CāH alkynylation.
Scheme 10: Late-stage Mn-catalyzed CāH allylation of peptides and bioactive motifs.
Scheme 11: Intramolecular CāH allylative cyclic peptide formation.
Scheme 12: Late-stage CāH glycosylation of tryptophan analogues.
Scheme 13: Late-stage CāH glycosylation of tryptophan-containing peptides.
Scheme 14: Late-stage CāH alkenylation of tryptophan-containing peptides.
Scheme 15: A) Late-stage CāH macrocyclization of tryptophan-containing peptides and B) traceless removal of py...
Beilstein J. Org. Chem. 2021, 17, 1565ā1590, doi:10.3762/bjoc.17.112
Graphical Abstract
Figure 1: Some examples of natural products and drugs containing quaternary carbon centers.
Scheme 1: Simplified mechanism for olefin hydrofunctionalization using an electrophilic transition metal as a...
Scheme 2: Selected examples of quaternary carbon centers formed by the intramolecular hydroalkylation of β-di...
Scheme 3: Control experiments and the proposed mechanism for the Pd(II)-catalyzed intermolecular hydroalkylat...
Scheme 4: Intermolecular olefin hydroalkylation of less reactive ketones under Pd(II) catalysis using HCl as ...
Scheme 5: A) Selected examples of Pd(II)-mediated quaternary carbon center synthesis by intermolecular hydroa...
Scheme 6: Selected examples of quaternary carbon center synthesis by gold(III) catalysis. This is the first r...
Scheme 7: Selected examples of inter- (A) and intramolecular (B) olefin hydroalkylations promoted by a silver...
Scheme 8: A) Intermolecular hydroalkylation of N-alkenyl β-ketoamides under Au(I) catalysis in the synthesis ...
Scheme 9: Asymmetric pyrrolidine synthesis through intramolecular hydroalkylation of α-substituted N-alkenyl ...
Scheme 10: Proposed mechanism for the chiral gold(I) complex promotion of the intermolecular olefin hydroalkyl...
Scheme 11: Selected examples of carbon quaternary center synthesis by gold and evidence of catalytic system pa...
Scheme 12: Synthesis of a spiro compound via an aza-Michael addition/olefin hydroalkylation cascade promoted b...
Scheme 13: A selected example of quaternary carbon center synthesis using an Fe(III) salt as a catalyst for th...
Scheme 14: Intermolecular hydroalkylation catalyzed by a cationic iridium complex (Fuji (2019) [47]).
Scheme 15: Generic example of an olefin hydrofunctionalization via MHAT (Shenvi (2016) [51]).
Scheme 16: The first examples of olefin hydrofunctionalization run under neutral conditions (Mukaiyama (1989) [56]...
Scheme 17: A) Aryl olefin dimerization catalyzed by vitamin B12 and triggered by HAT. B) Control experiment to...
Scheme 18: Generic example of MHAT diolefin cycloisomerization and possible competitive pathways. Shenvi (2014...
Scheme 19: Selected examples of the MHAT-promoted cycloisomerization reaction of unactivated olefins leading t...
Scheme 20: Regioselective carbocyclizations promoted by an MHAT process (Norton (2008) [76]).
Scheme 21: Selected examples of quaternary carbon centers synthetized via intra- (A) and intermolecular (B) MH...
Scheme 22: A) Proposed mechanism for the Fe(III)/PhSiH3-promoted radical conjugate addition between olefins an...
Scheme 23: Examples of cascade reactions triggered by HAT for the construction of trans-decalin backbone uniti...
Scheme 24: A) Selected examples of the MHAT-promoted radical conjugate addition between olefins and p-quinone ...
Scheme 25: A) MHAT triggered radical conjugate addition/E1cB/lactonization (in some cases) cascade between ole...
Scheme 26: A) Spirocyclization promoted by Fe(III) hydroalkylation of unactivated olefins. B) Simplified mecha...
Scheme 27: A) Selected examples of the construction of a carbon quaternary center by the MHAT-triggered radica...
Scheme 28: Hydromethylation of unactivated olefins under iron-mediated MHAT (Baran (2015) [95]).
Scheme 29: The hydroalkylation of unactivated olefins via iron-mediated reductive coupling with hydrazones (Br...
Scheme 30: Selected examples of the Co(II)-catalyzed bicyclization of dialkenylarenes through the olefin hydro...
Scheme 31: Proposed mechanism for the bicyclization of dialkenylarenes triggered by a MHAT process (Vanderwal ...
Scheme 32: Enantioconvergent cross-coupling between olefins and tertiary halides (Fu (2018) [108]).
Scheme 33: Proposed mechanism for the Ni-catalyzed cross-coupling reaction between olefins and tertiary halide...
Scheme 34: Proposed catalytic cycles for a MHAT/Ni cross-coupling reaction between olefins and halides (Shenvi...
Scheme 35: Selected examples of the hydroalkylation of olefins by a dual catalytic Mn/Ni system (Shenvi (2019) ...
Scheme 36: A) Selected examples of quaternary carbon center synthesis by reductive atom transfer; TBC: 4-tert-...
Scheme 37: A) Selected examples of quaternary carbon centers synthetized by radical addition to unactivated ol...
Scheme 38: A) Selected examples of organophotocatalysis-mediated radical polyene cyclization via a PET process...
Scheme 39: A) Sc(OTf)3-mediated carbocyclization approach for the synthesis of vicinal quaternary carbon cente...
Scheme 40: Scope of the Lewis acid-catalyzed methallylation of electron-rich styrenes. Method A: B(C6F5)3 (5.0...
Scheme 41: The proposed mechanism for styrene methallylation (Oestreich (2019) [123]).
Beilstein J. Org. Chem. 2021, 17, 977ā982, doi:10.3762/bjoc.17.79
Graphical Abstract
Figure 1: Biologically relevant 2-oxydibenzofuran-containing structures 1ā6.
Figure 2: Representative bioactive structures containing benzofuro-fused pyridine analogues 7ā9.
Scheme 1: Strategy for metal-free access to benzofuropyridine 13.
Scheme 2: Electrophilic aromatic substitution of 6-hydroxybenzofuro[2,3-b]pyridine (13).
Scheme 3: Synthesis of isomeric oxazole-fused derivatives.
Scheme 4: Fused derivatives from 16.