Search for "phosphine ligand" in Full Text gives 65 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2024, 20, 3256–3262, doi:10.3762/bjoc.20.269
Graphical Abstract
Figure 1: Structures of multiply fused heterocyclic compounds composed of pyridine rings.
Scheme 1: Synthesis of C–H arylation precursors 1a–c.
Scheme 2: Palladium-catalyzed intramolecular direct arylation for synthesizing 8a and 8b and the X-ray crysta...
Beilstein J. Org. Chem. 2024, 20, 1973–1980, doi:10.3762/bjoc.20.173
Graphical Abstract
Scheme 1: (a) Sequential π-Lewis acidic metal-catalyzed cyclization/photochemical radical addition for the fo...
Scheme 2: The reaction with benzyltrimethylsilane derivatives 2. aFlow rate was 6 mL/h and premixing zone was...
Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98
Graphical Abstract
Scheme 1: General scheme of the borrowing hydrogen (BH) or hydrogen auto-transfer (HA) methodology.
Scheme 2: General scheme for C–N bond formation. A) Traditional cross-couplings with alkyl or aryl halides. B...
Figure 1: Manganese pre-catalysts used for the N-alkylation of amines with alcohols.
Scheme 3: Manganese(I)-pincer complex Mn1 used for the N-alkylation of amines with alcohols and methanol.
Scheme 4: N-Methylation of amines with methanol using Mn2.
Scheme 5: C–N-Bond formation with amines and methanol using PN3P-Mn complex Mn3 reported by Sortais et al. [36]. a...
Scheme 6: Base-assisted synthesis of amines and imines with Mn4. Reaction assisted by A) t-BuOK and B) t-BuON...
Scheme 7: Coupling of alcohols and hydrazine via the HB approach reported by Milstein et al. [38]. aReaction time...
Scheme 8: Proposed mechanism for the coupling of alcohols and hydrazine catalyzed by Mn5.
Scheme 9: Phosphine-free manganese catalyst for N-alkylation of amines with alcohols reported by Balaraman an...
Scheme 10: N-Alkylation of sulfonamides with alcohols.
Scheme 11: Mn–NHC catalyst Mn6 applied for the N-alkylation of amines with alcohols. a3 mol % of Mn6 were used....
Scheme 12: N-Alkylation of amines with primary and secondary alcohols. a80 °C, b100 °C.
Scheme 13: Manganese(III)-porphyrin catalyst for synthesis of tertiary amines.
Scheme 14: Proposed mechanism for the alcohol dehydrogenation with Mn(III)-porphyrin complex Mn7.
Scheme 15: N-Methylation of nitroarenes with methanol using catalyst Mn3.
Scheme 16: Mechanism of manganese-catalyzed methylation of nitroarenes using Mn3 as the catalyst.
Scheme 17: Bidentate manganese complex Mn8 applied for the N-alkylation of primary anilines with alcohols. aOn...
Scheme 18: N-Alkylation of amines with alcohols in the presence of manganese salts and triphenylphosphine as t...
Scheme 19: N-Alkylation of diazo compounds with alcohols using catalyst Mn9.
Scheme 20: Proposed mechanism for the amination of alcohols with diazo compounds catalyzed by catalyst Mn9.
Scheme 21: Mn1 complex-catalyzed synthesis of polyethyleneimine from ethylene glycol and ethylenediamine.
Scheme 22: Bis-triazolylidene-manganese complex Mn10 for the N-alkylation of amines with alcohols.
Figure 2: Manganese complexes applied for C-alkylation reactions of ketones with alcohols.
Scheme 23: General scheme for the C–C bond formation with alcohols and ketones.
Scheme 24: Mn1 complex-catalyzed α-alkylation of ketones with primary alcohols.
Scheme 25: Mechanism for the Mn1-catalyzed alkylation of ketones with alcohols.
Scheme 26: Phosphine-free in situ-generated manganese catalyst for the α-alkylation of ketones with primary al...
Scheme 27: Plausible mechanism for the Mn-catalyzed α-alkylation of ketones with alcohols.
Scheme 28: α-Alkylation of esters, ketones, and amides using alcohols catalyzed by Mn11.
Scheme 29: Mono- and dialkylation of methylene ketones with primary alcohols using the Mn(acac)2/1,10-phenanth...
Scheme 30: Methylation of ketones with methanol and deuterated methanol.
Scheme 31: Methylation of ketones and esters with methanol. a50 mol % of t-BuOK were used, bCD3OD was used ins...
Scheme 32: Alkylation of ketones and secondary alcohols with primary alcohols using Mn4.
Scheme 33: Bidentate manganese-NHC complex Mn6 applied for the synthesis of alkylated ketones using alcohols.
Scheme 34: Mn1-catalyzed synthesis of substituted cycloalkanes by coupling diols and secondary alcohols or ket...
Scheme 35: Proposed mechanism for the synthesis of cycloalkanes via BH method.
Scheme 36: Synthesis of various cycloalkanes from methyl ketones and diols catalyze by Mn13. aReaction time wa...
Scheme 37: N,N-Amine–manganese complex (Mn13)-catalyzed alkylation of ketones with alcohols.
Scheme 38: Naphthyridine‑N‑oxide manganese complex Mn14 applied for the alkylation of ketones with alcohols. a...
Scheme 39: Proposed mechanism of the naphthyridine‑N‑oxide manganese complex (Mn14)-catalyzed alkylation of ke...
Scheme 40: α-Methylation of ketones and indoles with methanol using Mn15.
Scheme 41: α-Alkylation of ketones with primary alcohols using Mn16. aNMR yield.
Figure 3: Manganese complexes used for coupling of secondary and primary alcohols.
Scheme 42: Alkylation of secondary alcohols with primary alcohols catalyzed by phosphine-free catalyst Mn17. a...
Scheme 43: PNN-Manganese complex Mn18 for the alkylation of secondary alcohols with primary alcohols.
Scheme 44: Mechanism for the Mn-pincer catalyzed C-alkylation of secondary alcohols with primary alcohols.
Scheme 45: Upgrading of ethanol with methanol for isobutanol production.
Scheme 46: Mn-Pincer catalyst Mn19 applied for the β-methylation of alcohols with methanol. a2.0 mol % of Mn19...
Scheme 47: Functionalized ketones from primary and secondary alcohols catalyzed by Mn20. aMn20 (5 mol %), NaOH...
Scheme 48: Synthesis of γ-disubstituted alcohols and β-disubstituted ketones through Mn9-catalyzed coupling of...
Scheme 49: Proposed mechanism for the Mn9-catalyzed synthesis of γ-disubstituted alcohols and β-disubstituted ...
Scheme 50: Dehydrogenative coupling of ethylene glycol and primary alcohols catalyzed by Mn4.
Scheme 51: Mn18-cataylzed C-alkylation of unactivated esters and amides with alcohols.
Scheme 52: Alkylation of amides and esters using Mn21.
Scheme 53: α-Alkylation of nitriles with primary alcohols using in situ-generated manganese catalyst.
Scheme 54: Proposed mechanism for the α-alkylation of nitriles with primary alcohols.
Scheme 55: Mn9-catalyzed α-alkylation of nitriles with primary alcohols. a1,4-Dioxane was used as solvent, 24 ...
Figure 4: Manganese complexes used for alkylation of heterocyclic compounds.
Scheme 56: Aminomethylation of aromatic compounds with secondary amines and methanol catalyzed by Mn22.
Scheme 57: Regioselective alkylation of indolines with alcohols catalyzed by Mn9. aMn9 (4 mol %), 48 h.
Scheme 58: Proposed mechanism for the C- and N-alkylation of indolines with alcohols.
Scheme 59: C-Alkylation of methyl N-heteroarenes with primary alcohols catalyzed by Mn1. aTime was 60 h.
Scheme 60: C-Alkylation of oxindoles with secondary alcohols.
Scheme 61: Plausible mechanism for the Mn23-catalyzed C-alkylation of oxindoles with secondary alcohols.
Scheme 62: Synthesis of C-3-alkylated products by coupling alcohols with indoles and aminoalcohols.
Scheme 63: C3-Alkylation of indoles using Mn1.
Scheme 64: C-Methylation of indoles with Mn15 and methanol.
Scheme 65: α-Alkylation of 2-oxindoles with primary and secondary alcohols catalyzed by Mn25. aReaction carrie...
Scheme 66: Dehydrogenative alkylation of indolines with Mn1. aMn1 (5.0 mol %) was used.
Scheme 67: Synthesis of bis(indolyl)methane derivatives from indoles and alcohols catalyzed by Mn26. aMn26 (5....
Scheme 68: One-pot synthesis of pyrimidines via BH.
Scheme 69: Synthesis of pyrroles from alcohols and aminoalcohols using Mn4.
Scheme 70: Synthesis of pyrroles via multicomponent reaction catalyzed by Mn12.
Scheme 71: Friedländer quinoline synthesis using an in situ-generated phosphine-free manganese catalyst.
Scheme 72: Quinoline synthesis using bis-N-heterocyclic carbene-manganese catalyst Mn6.
Scheme 73: Quinoline synthesis using manganese(III)-porphyrin catalyst Mn7.
Scheme 74: Manganese-catalyzed tetrahydroquinoline synthesis via borrowing BH.
Scheme 75: Proposed mechanism for the manganese-catalyzed tetrahydroquinoline synthesis.
Scheme 76: Synthesis of C3-alkylated indoles using Mn24.
Scheme 77: Synthesis of C-3-alkylated indoles using Mn1.
Scheme 78: C–C Bond formation by coupling of alcohols and ylides.
Scheme 79: C-Alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 80: Proposed mechanism for the C-alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 81: α-Alkylation of sulfones using Mn-PNN catalyst Mn28.
Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43
Graphical Abstract
Scheme 1: Proposed mechanism and observation of alkylgold intermediates.
Figure 1: First order alkene decay for urea alkene 1a (0.05 M) hydroamination with [JPhosAu(NCCH3)]SbF6 (5, 2...
Figure 2: Cooperative effect of mixed CD2Cl2/MeOH on alkene 1a → 3a conversion with catalyst 5 (2.5 mol %). E...
Figure 3: Different additive impact on rate of 1a → 3a depending upon catalyst and co-solvent. The data for J...
Figure 4: (a) Schematic for synthesis of [L–Au–L]SbF6 where L = JPhos. (b) Perspective drawing of the cation ...
Figure 5: (a) kobs for reaction of urea 1a (0.05 M) in DCM with catalyst 5 and titrated CH3OH/CH3OD. Data for...
Figure 6: Rate of urea 1a (0.05 M) hydroamination with JPhosAu(NCCH3)SbF6 (2.5 mol %) in CH2Cl2 with 5, 25, a...
Figure 7: Observed rates for the reaction of carbamate 1b (0.03–0.24 M) with JackiephosAuNTf2 (0.0013 M, 6a) ...
Figure 8: Influence of catalyst 5 concentration on rate of 1a (0.05 M in CH2Cl2 with 0, 10 μL MeOH). Error ba...
Scheme 2: Proposed alternate mechanism.
Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37
Graphical Abstract
Figure 1: Structure of fluoranthene.
Scheme 1: Pd-catalyzed access to fluoranthenes.
Scheme 2: Scope of the Pd-catalyzed direct arylation reaction of arenes with 1,8-dibromonaphthalene.
Scheme 3: Scope of the Pd-catalyzed direct arylation reaction of 2,5-substituted heteroarenes with 1,8-dibrom...
Scheme 4: Scope of the Pd-catalyzed Suzuki reaction followed by direct arylation of arylboronic acids with 1,...
Scheme 5: Attempted reaction of 1-naphthylboronic acid with 1,2-dihalobenzenes.
Scheme 6: Pd-catalyzed Heck reaction followed by direct arylation of 1,1-diphenylethylene with 1,2-dihalobenz...
Beilstein J. Org. Chem. 2024, 20, 272–279, doi:10.3762/bjoc.20.28
Graphical Abstract
Scheme 1: Rhodium(I)-catalyzed cycloaddition of C60 with diynes to afford bis(fulleroid) derivatives [33].
Figure 1: Types of [6,6]-bonds together with the [5,6]-bond of C60 with their C–C distances in pristine C60 a...
Scheme 2: Rhodium-catalyzed cycloaddition of C70 with diynes 1a and 1b.
Figure 2: 1H NMR (CS2/CDCl3, 400 MHz) spectrum of compound 2a as a mixture of two isomers.
Figure 3: B3LYP-D3/cc-pVTZ-PP(SMD=o-DCB)//B3LYP-D3/CC-pVDZ-PP Gibbs energy profile of the [2 + 2 + 2] cycload...
Scheme 3: Oxidative cleavage of bis(fulleroid) derivatives 2a and 2b.
Figure 4: 1H NMR (CS2/CDCl3, 400 MHz) spectrum of compound 3a as a mixture of three isomers. X = residual tol...
Beilstein J. Org. Chem. 2023, 19, 582–592, doi:10.3762/bjoc.19.43
Graphical Abstract
Scheme 1: C3-Functionalization of furfural derivatives by C–H activation, a) in batch: previous works, and b)...
Scheme 2: C3-alkylation of bidentate imine 1 performed in batch.
Scheme 3: Optimization of the heating for the alkylation reaction on the homemade pulsed-flow setup.
Scheme 4: Proposed reaction mechanism for the alkylation reaction with formation of ruthenium aggregates and ...
Scheme 5: A) Isolation test of a reaction intermediate; B) XPS and TEM (in ethanol) of the recovered solid ph...
Scheme 6: Ruthenium aggregate-catalyzed alkylation reaction.
Scheme 7: Scope of continuous flow furfural derivative alkylation reaction.
Scheme 8: Scaling up comparison: batch and continuous flow conditions.
Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38
Graphical Abstract
Figure 1: Ring-strain energies of homobicyclic and heterobicyclic alkenes in kcal mol−1. 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 C–H 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 C–H 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 C–H 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 C–C/C–N 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-Diels–Alder 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-Diels–Alder 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. 2022, 18, 190–196, doi:10.3762/bjoc.18.21
Graphical Abstract
Figure 1: Selected examples of: a) calix[4]arene-; b) resorcin[4]arene-; c) calix[6]arene-gold(I) macrocyclic...
Scheme 1: i) NH2NH2∙H2O, Pd/C in EtOH, 80 °C (quant.); ii) diphenylphosphinobenzoic acid, EDC∙HCl, DMAP (cat....
Figure 2: Stacked-plot, mid-field expanded region of the 1H NMR spectrum (400 MHz, 298 K) of A(AuCl)2, B(AuCl)...
Figure 3: Stacked plot 1H NMR (tetrachloroethane-d2) of A(AuCl)2 at variable temperature.
Scheme 2: Synthesis of the monomeric gold catalyst analogues A’,B’,C’(AuCl). Conditions: i) diphenylphosphino...
Beilstein J. Org. Chem. 2021, 17, 2102–2122, doi:10.3762/bjoc.17.137
Graphical Abstract
Scheme 1: Synthesis of 2,2’-bis(indole)borinic ester 3.
Scheme 2: Synthesis of 2,2’-bisindole NHC·boranes by an SEAr mechanism.
Scheme 3: Syntheses of indolyl amines through Buchwald–Hartwig cross coupling.
Scheme 4: Synthesis of 3,3’-bis(indolyl) ethers.
Scheme 5: C–H silylation of indoles.
Scheme 6: n-BuLi-mediated syntheses of bis(indol-3-yl)silanes.
Scheme 7: Acid-catalyzed syntheses of bis(indol-3-yl)silanes and mechanisms.
Scheme 8: B(C6F5)3 and Al(C6F5)3-catalyzed syntheses of bis(indol-3-yl)silanes reported by Han.
Scheme 9: Base-mediated syntheses of bis and tris(indol-2-yl)phosphines.
Scheme 10: Synthesis of bis(indol-2-yl)sulfides using SL2-type reagents.
Scheme 11: Synthesis of 2,3’- and 2,2’-bis(indolyl)sulfides using disulfides as substrates.
Scheme 12: Synthesis of diindol-2-ylsulfide (84) from 2-iodoindole (92) and thiourea.
Scheme 13: Synthesis of bis(indol-3-yl)sulfides using N-silylated 3-bromoindole 93.
Scheme 14: Fischer indole synthesis of bis(indol-3-yl)sulfides using thio diketones.
Scheme 15: Oxidative synthesis of bis(indol-3-yl)sulfides using indoles and elemental sulfur.
Scheme 16: Synthesis of bis(indol-3-yl)sulfides using sulfoxides as sulfur source.
Scheme 17: Syntheses of bis(indol-2-yl)selanes.
Scheme 18: Syntheses of bis(indol-3-yl)selanes.
Scheme 19: Synthesis of bis(indol-2-yl)tellane 147.
Scheme 20: Synthesis of tris(indolyl)borane 154.
Scheme 21: Synthesis of bis(indol-4-yl)amines 159.
Scheme 22: Synthesis of bis(indol-5-yl)amines.
Scheme 23: Synthesis of 6,5’/6,6’-bis(indolyl)amines.
Scheme 24: Synthesis of potent HIV-inhibitors 6,6’-bis(indolyl) ethers.
Scheme 25: Synthesis of bis(indol-7-yl) ether.
Scheme 26: Synthesis of di(indol-5-yl)sulfide (183).
Scheme 27: Syntheses of 2,2’-diformyl-7,7’-bis(indolyl)selenides.
Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84
Graphical Abstract
Scheme 1: Synthesis of optically pure 4-phenylchroman-2-one [34].
Scheme 2: Synthesis of (R)-tolterodine [3].
Scheme 3: Catalytic cycle of the Pd(II)-catalysed 1,4-addition of organoboron reagents to enones [3,26,35].
Scheme 4: Enantioselective β-arylation of cyclohexanone [38].
Scheme 5: Application of L2/Pd(OAc)2 in the total synthesis of terpenes [8].
Scheme 6: Plausible catalytic cycle for the addition of phenylboronic acid to 2-cyclohexenone catalysed by L3...
Scheme 7: Microwave-assisted addition of phenylboronic acid to 2-cyclohexenone catalysed by L4/Pd2(dba)3·CHCl3...
Scheme 8: Plausible catalytic cycle of the addition of phenylboronic acid to 2-cyclohexenone catalysed by pal...
Scheme 9: Proposed catalytic cycle for the addition of phenylboronic acids to 2-cyclohexenone catalysed by Pd...
Scheme 10: Usage of addition reactions of boronic acids to various chromones in the syntheses of potentially a...
Scheme 11: Multigram-scale synthesis of ABBV-2222 [6].
Scheme 12: Application of the asymmetric addition of phenylboronic acid to a chromone derivative for the total...
Scheme 13: Plausible catalytic cycle for the addition of phenylboronic acid to 3-methyl-2-cyclohexenone cataly...
Scheme 14: Total syntheses of naturally occurring terpenoids [10,11].
Scheme 15: Use of the L9/Pd(TFA)2 catalytic system for the synthesis of intermediates of biologically active c...
Scheme 16: Usage of a Michael addition catalysed by L9/Pd(TFA)2 in the total synthesis of (–)-ar-tenuifolene [12].
Scheme 17: Synthesis of terpenoids by Michael addition to 3-methyl-2-cyclopentenone [13].
Scheme 18: Rh-catalysed isomerisation of 3-alkyl-3-arylcyclopentanones to 1-tetralones [53].
Scheme 19: Addition reaction of phenylboronic acid to 3-methyl-2-cyclohexenone catalysed by L9/Pd(TFA)2 in wat...
Scheme 20: Micellar nanoreactor PdL10c for the synthesis of flavanones [58].
Scheme 21: Plausible catalytic cycle for the desymmetrisation of polycyclic cyclohexenediones by the addition ...
Scheme 22: Attempt to use the catalytic system L2/Pd(TFA)2 for the addition of phenylboronic acid to 3-methyl-...
Scheme 23: Ring opening of an enantioenriched tetrahydropyran-2-one derivative as alternative strategy to line...
Scheme 24: Synthesis of biologically active compounds from addition products [14-16].
Scheme 25: Chiral 1,10-phenantroline derivative L15 as ligand for the Pd-catalysed addition reactions of pheny...
Scheme 26: The Rh-catalysed addition reaction of phenylboronic acid to a 3-substituted enone [20].
Scheme 27: Underdeveloped methodologies [14,15,65-67].
Scheme 28: Flowchart for the selection of the proper catalytic system.
Beilstein J. Org. Chem. 2020, 16, 3015–3031, doi:10.3762/bjoc.16.251
Graphical Abstract
Figure 1: Highly-substituted five-membered carbocycle in biologically significant natural products.
Figure 2: Natural product synthesis featuring the all-carbon [3 + 2] cycloaddition. (Quaternary carbon center...
Scheme 1: Representative natural product syntheses that feature the all-carbon [3 + 2] cyclization as the key...
Scheme 2: (A) An intramolecular trimethylenemethane diyl [3 + 2] cycloaddition with allenyl diazo compound 38...
Scheme 3: (A) Palladium-catalyzed intermolecular carboxylative TMM cycloaddition [36]. (B) The proposed mechanism....
Scheme 4: Natural product syntheses that make use of palladium-catalyzed intermolecular [3 + 2] cycloaddition...
Scheme 5: (A) Phosphine-catalyzed [3 + 2] cycloaddition [17]. (B) The proposed mechanism.
Scheme 6: Lu’s [3 + 2] cycloaddition in natural product synthesis. (A) Synthesis of longeracinphyllin A (10) [41]...
Scheme 7: (A) Phosphine-catalyzed [3 + 2] annulation of unsymmetric isoindigo 100 with allene in the preparat...
Scheme 8: (A) Rhodium-catalyzed intracmolecular [3 + 2] cycloaddition [49]. (B) The proposed catalytic cycle of t...
Scheme 9: Total synthesis of natural products reported by Yang and co-workers applying rhodium-catalyzed intr...
Scheme 10: (A) Platinum(II)-catalyzed intermolecular [3 + 2] cycloaddition of propargyl ether 139 and n-butyl ...
Scheme 11: (A) Platinum-catalyzed intramolecular [3 + 2] cycloaddition of propargylic ketal derivative 142 to ...
Scheme 12: (A) Synthesis of phyllocladanol (21) features a Lewis acid-catalyzed formal intramolecular [3 + 2] ...
Scheme 13: The recent advances of [3 + 2] annulation in natural product synthesis. (A) The preparation of melo...
Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186
Graphical Abstract
Figure 1: Representation of corannulene (1) and sumanene (2), the subunits of fullerene (C60).
Scheme 1: Mehta’s unsuccessful effort for the synthesis of sumanene scaffold 2.
Scheme 2: First synthesis of sumanene 2 by Sakurai et al. from norbornadiene 10.
Scheme 3: Synthesis of trimethylsumanene 28 from easily accessible norbornadiene (10).
Scheme 4: Generation of anions 29–31 and the preparation of tris(trimethylsilyl)sumanene 32.
Scheme 5: Synthesis of tri- and hexa-substituted sumanene derivatives.
Scheme 6: Synthesis of bowl-shaped π-extended sumanene derivatives 37a–f.
Scheme 7: Synthesis of monooxasumanene 38, trioxosumanene 40 along with imination of them.
Scheme 8: Synthesis of trimethylsumanenetrione 46 and exo-functionalized products 45a,b.
Scheme 9: Synthesis of bisumanenylidene 47 and sumanene dimer 48 from 2.
Scheme 10: The mono-substitution of 2 to generate diverse mono-sumanene derivatives 49a–d.
Scheme 11: Synthesis of sumanene building block 53 useful for further extension.
Scheme 12: Synthesis of hexafluorosumanene derivative 55 by Sakurai and co-workers.
Scheme 13: Preparation of sumanene-based carbene 60 and its reaction with cyclohexane.
Scheme 14: Barton–Kellogg reaction for the synthesis of sterically hindered alkenes.
Scheme 15: Synthesis of hydroxysumanene 68 by employing Baeyer–Villiger oxidation.
Scheme 16: Synthesis of sumanene derivatives having functionality at an internal carbon.
Scheme 17: Mechanism for nucleophilic substitution reaction at the internal carbon.
Scheme 18: Synthesis of diverse monosubstituted sumanene derivatives.
Scheme 19: Synthesis of di- and trisubstituted sumanene derivatives from sumanene (2).
Scheme 20: Preparation of monochlorosumanene 88 and hydrogenation of sumanene (2).
Scheme 21: The dimer 90 and bissumanenyl 92 achieved from halosumannes.
Scheme 22: Pyrenylsumanene 93 involving the Suzuki-coupling as a key transformation.
Scheme 23: Synthesis of various hexaarylsumanene derivatives using the Suzuki-coupling reaction.
Scheme 24: Synthesis of hexasubstituted sumanene derivatives 96 and 97.
Scheme 25: Synthesis of thioalkylsumanenes via an aromatic nucleophilic substitution reaction.
Scheme 26: Synthesis of tris(ethoxycarbonylethenyl)sumanene derivative 108.
Scheme 27: Synthesis of ferrocenyl-based sumanene derivatives.
Scheme 28: Synthesis of sumanenylferrocene architectures 118 and 119 via Negishi coupling.
Scheme 29: Diosmylation and the synthesis of phenylboronate ester 121 of sumanene.
Scheme 30: Synthesis of the iron-complex of sumanene.
Scheme 31: Synthesis of tri- and mononuclear sumanenyl zirconocene complexes.
Scheme 32: Synthesis of [CpRu(η6-sumanene)]PF6.
Scheme 33: Preparation of sumanene-based porous coordination networks 127 (spherical tetramer units) and 128 (...
Scheme 34: Synthesis of sumanenylhafnocene complexes 129 and 130.
Scheme 35: Synthesis of 134 and 135 along with PdII coordination complex 136.
Scheme 36: Synthesis of alkali metals sumanene complex K7(C21H102−)2(C21H93−)·8THF (137) containing di- and tr...
Scheme 37: The encapsulation of a Cs+ ion between two sumanenyl anions.
Scheme 38: Synthesis of monothiasumanene 140 and dithiasumanene 141 from 139.
Scheme 39: Synthesis of trithiasumanene 151 by Otsubo and his co-workers.
Scheme 40: Synthesis of trithiasumanene derivatives 155 and 156.
Scheme 41: Synthetic route towards hexathiolated trithiasumanenes 158.
Scheme 42: Synthesis of triselenasumanene 160 by Shao and teammates.
Scheme 43: Synthesis of tritellurasumanene derivatives from triphenylene skeletons.
Scheme 44: Synthesis of pyrazine-fused sumanene architectures through condensation reaction.
Scheme 45: Treatment of the trichalcogenasumanenes with diverse oxidative reagents.
Scheme 46: Ring-opening reaction with H2O2 and oxone of heterasumanenes 178 and 179.
Scheme 47: Synthesis of polycyclic compounds from sumanene derivatives.
Scheme 48: Synthesis of diimide-based heterocycles reported by Shao’s and co-workers.
Scheme 49: Synthesis of pristine trichalcogenasumanenes, 151, 205, and 206.
Scheme 50: Synthesis of trichalcogenasumanenes via hexaiodotriphenylene precursor 208.
Scheme 51: Synthesis of trisilasumanenes 214 and 215.
Scheme 52: Synthesis of trisilasumanene derivatives 218 and 219.
Scheme 53: Synthesis of novel trigermasumanene derivative 223.
Scheme 54: An attempt towards the synthesis of tristannasumanene derivative 228.
Scheme 55: Synthesis of triphosphasumanene trisulfide 232 from commercially available 229.
Scheme 56: The doping of sumanene derivatives with chalcogens (S, Se, Te) and phosphorus.
Scheme 57: Synthesis of heterasumanene containing three different heteroatoms.
Scheme 58: Synthesis of trichalcogenasumanene derivatives 240 and 179.
Scheme 59: Preparation of trichalcogenasumanenes 245 and 248.
Scheme 60: Design and synthesis of trichalcogenasumanene derivatives 252 and 178.
Scheme 61: Synthesis of spirosumanenes 264–269 and non-spiroheterasumanenes 258–263.
Scheme 62: Synthesis of sumanene-type hetero polycyclic compounds.
Scheme 63: Synthesis of triazasumanenes 288 and its sulfone congener 287.
Scheme 64: Synthesis of C3-symmetric chiral triaryltriazasumanenes via cross-coupling reaction.
Scheme 65: Synthesis of mononaphthosumanene 293 using Suzuki coupling as a key step.
Scheme 66: Synthesis of di- and trinaphthosumanene derivatives 302–304.
Scheme 67: Synthesis of hemifullerene skeletons by Hirao’s group.
Scheme 68: Design and construction of C70 fragment from a C60 sumanene fragment.
Beilstein J. Org. Chem. 2020, 16, 2193–2200, doi:10.3762/bjoc.16.184
Graphical Abstract
Figure 1: Indenol skeleton.
Scheme 1: Synthesis of 2,3-disubstituted indene derivatives.
Scheme 2: Cobalt-catalyzed [2 + 3] cycloaddition reaction of the fluorinated alkynes 1 with various 2-formylp...
Scheme 3: Synthesis of the fluoroalkylated indenone 6 and the indanone 7 from the indenol 3aA. The yields wer...
Scheme 4: Stereochemical assignment of 5aA and 7 based on NMR techniques. The cross-peaks were observed throu...
Scheme 5: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2020, 16, 1924–1935, doi:10.3762/bjoc.16.159
Graphical Abstract
Scheme 1: Synthesis of NHC-supported catalysts.
Scheme 2: Negishi benchmark reaction.
Figure 1: Negishi reaction catalyzed by immobilized NHC–Pd complexes. Conditions: methyl 4-bromobenzoate (0.2...
Scheme 3: Synthesis of immobilized NHC–Pd–RuPhos.
Figure 2: Negishi model reaction between 5 and 6 under flow conditions catalyzed by 4b. V = 0.535 mL, 363 mg ...
Figure 3: Negishi model reaction under flow conditions catalyzed by 8a. V = 2.9 mL, 1.25 g of catalyst, resid...
Figure 4: Negishi reaction between 5 and 6 catalyzed by 8a in the presence of SILLPs. a) Yield (%) vs time fo...
Figure 5: TEM images of the polymers after the Negishi reaction between 5 and 6. a) 8a, bar scale 20 nm, PdNP...
Scheme 4: Pd species immobilized onto SILLPs. i) 1 g SILLP 10, 100 mg PdCl2 in milli-Q® water (100 mL 1% HCl,...
Figure 6: Negishi reaction between 5 and 6 catalyzed by 11. 1 equiv methyl 4-bromobenzoate (6, 0.25 mmol), 2 ...
Figure 7: Negishi reaction between 5 and 6 under flow conditions catalyzed by 8a in the presence of a scaveng...
Figure 8: Effect of the structure of the SILLP scavenger for the Negishi reaction between 5 and 6 under flow ...
Figure 9: TEM images of the polymer after the Negishi reaction between 5 and 6 under flow conditions. a) 8a + ...
Beilstein J. Org. Chem. 2020, 16, 691–737, doi:10.3762/bjoc.16.67
Graphical Abstract
Scheme 1: Pharmaceuticals possessing a silicon or boron atom.
Scheme 2: The first Cu-catalyzed C(sp3)–Si bond formation.
Scheme 3: Conversion of benzylic phosphate 6 to the corresponding silane.
Scheme 4: Conversion of alkyl triflates to alkylsilanes.
Scheme 5: Conversion of secondary alkyl triflates to alkylsilanes.
Scheme 6: Conversion of alkyl iodides to alkylsilanes.
Scheme 7: Trapping of intermediate radical through cascade reaction.
Scheme 8: Radical pathway for conversion of alkyl iodides to alkylsilanes.
Scheme 9: Conversion of alkyl ester of N-hydroxyphthalimide to alkylsilanes.
Scheme 10: Conversion of gem-dibromides to bis-silylalkanes.
Scheme 11: Conversion of imines to α-silylated amines (A) and the reaction pathway (B).
Scheme 12: Conversion of N-tosylimines to α-silylated amines.
Scheme 13: Screening of diamine ligands.
Scheme 14: Conversion of N-tert-butylsulfonylimines to α-silylated amines.
Scheme 15: Conversion of aldimines to nonracemic α-silylated amines.
Scheme 16: Conversion of N-tosylimines to α-silylated amines.
Scheme 17: Reaction pathway [A] and conversion of aldehydes to α-silylated alcohols [B].
Scheme 18: Conversion of aldehydes to benzhydryl silyl ethers.
Scheme 19: Conversion of ketones to 1,2-diols (A) and conversion of imines to 1,2-amino alcohols (B).
Scheme 20: Ligand screening (A) and conversion of aldehydes to α-silylated alcohols (B).
Scheme 21: Conversion of aldehydes to α-silylated alcohols.
Scheme 22: 1,4-Additions to α,β-unsaturated ketones.
Scheme 23: 1,4-Additions to unsaturated ketones to give β-silylated derivatives.
Scheme 24: Additions onto α,β-unsaturated lactones to give β-silylated lactones.
Scheme 25: Conversion of α,β-unsaturated to β-silylated lactams.
Scheme 26: Conversion of N-arylacrylamides to silylated oxindoles.
Scheme 27: Conversion of α,β-unsaturated carbonyl compounds to silylated tert-butylperoxides.
Scheme 28: Catalytic cycle for Cu(I) catalyzed α,β-unsaturated compounds.
Scheme 29: Conversion of p-quinone methides to benzylic silanes.
Scheme 30: Conversion of α,β-unsaturated ketimines to regio- and stereocontrolled allylic silanes.
Scheme 31: Conversion of α,β-unsaturated ketimines to enantioenriched allylic silanes.
Scheme 32: Regioselective conversion of dienedioates to allylic silanes.
Scheme 33: Conversion of alkenyl-substituted azaarenes to β-silylated adducts.
Scheme 34: Conversion of conjugated benzoxazoles to enantioenriched β-silylated adducts.
Scheme 35: Conversion of α,β-unsaturated carbonyl indoles to α-silylated N-alkylated indoles.
Scheme 36: Conversion of β-amidoacrylates to α-aminosilanes.
Scheme 37: Conversion of α,β-unsaturated ketones to enantioenriched β-silylated ketones, nitriles, and nitro d...
Scheme 38: Regio-divergent silacarboxylation of allenes.
Scheme 39: Silylation of diazocarbonyl compounds, (A) asymmetric and (B) racemic.
Scheme 40: Enantioselective hydrosilylation of alkenes.
Scheme 41: Conversion of 3-acylindoles to indolino-silanes.
Scheme 42: Proposed mechanism for the silylation of 3-acylindoles.
Scheme 43: Silyation of N-chlorosulfonamides.
Scheme 44: Conversion of acyl silanes to α-silyl alcohols.
Scheme 45: Conversion of N-tosylaziridines to β-silylated N-tosylamines.
Scheme 46: Conversion of N-tosylaziridines to silylated N-tosylamines.
Scheme 47: Conversion of 3,3-disubstituted cyclopropenes to silylated cyclopropanes.
Scheme 48: Conversion of conjugated enynes to 1,3-bis(silyl)propenes.
Scheme 49: Proposed sequence for the Cu-catalyzed borylation of substituted alkenes.
Scheme 50: Cu-catalyzed synthesis of nonracemic allylic boronates.
Scheme 51: Cu–NHC catalyzed synthesis of α-substituted allylboronates.
Scheme 52: Synthesis of α-chiral (γ-alkoxyallyl)boronates.
Scheme 53: Cu-mediated formation of nonracemic cis- or trans- 2-substituted cyclopropylboronates.
Scheme 54: Cu-catalyzed synthesis of γ,γ-gem-difluoroallylboronates.
Scheme 55: Cu-catalyzed hydrofunctionalization of internal alkenes and vinylarenes.
Scheme 56: Cu-catalyzed Markovnikov and anti-Markovnikov borylation of alkenes.
Scheme 57: Cu-catalyzed borylation/ortho-cyanation/Cope rearrangement.
Scheme 58: Borylfluoromethylation of alkenes.
Scheme 59: Cu-catalyzed synthesis of tertiary nonracemic alcohols.
Scheme 60: Synthesis of densely functionalized and synthetically versatile 1,2- or 4,3-borocyanated 1,3-butadi...
Scheme 61: Cu-catalyzed trifunctionalization of allenes.
Scheme 62: Cu-catalyzed selective arylborylation of arenes.
Scheme 63: Asymmetric borylative coupling between styrenes and imines.
Scheme 64: Regio-divergent aminoboration of unactivated terminal alkenes.
Scheme 65: Cu-catalyzed 1,4-borylation of α,β-unsaturated ketones.
Scheme 66: Cu-catalyzed protodeboronation of α,β-unsaturated ketones.
Scheme 67: Cu-catalyzed β-borylation of α,β-unsaturated imines.
Scheme 68: Cu-catalyzed synthesis of β-trifluoroborato carbonyl compounds.
Scheme 69: Asymmetric 1,4-borylation of α,β-unsaturated carbonyl compounds.
Scheme 70: Cu-catalyzed ACB and ACA reactions of α,β-unsaturated 2-acyl-N-methylimidazoles.
Scheme 71: Cu-catalyzed diborylation of aldehydes.
Scheme 72: Umpolung pathway for chiral, nonracemic tertiary alcohol synthesis (top) and proposed mechanism for...
Scheme 73: Cu-catalyzed synthesis of α-hydroxyboronates.
Scheme 74: Cu-catalyzed borylation of ketones.
Scheme 75: Cu-catalyzed borylation of unactivated alkyl halides.
Scheme 76: Cu-catalyzed borylation of allylic difluorides.
Scheme 77: Cu-catalyzed borylation of cyclic and acyclic alkyl halides.
Scheme 78: Cu-catalyzed borylation of unactivated alkyl chlorides and bromides.
Scheme 79: Cu-catalyzed decarboxylative borylation of carboxylic acids.
Scheme 80: Cu-catalyzed borylation of benzylic, allylic, and propargylic alcohols.
Beilstein J. Org. Chem. 2020, 16, 645–656, doi:10.3762/bjoc.16.61
Graphical Abstract
Figure 1: Rhodium-catalyzed reductive carbonylation of iodobenzene with CO and H2 to afford benzaldehyde. a) ...
Scheme 1: Scaled-up experiment of the reductive carbonylation of iodobenzene to benzaldehyde under the optimi...
Scheme 2: Catalytic species participating in the catalytic process.
Scheme 3: Substrate scope for the Rh-catalyzed reductive carbonylation of aryl iodides using CO and H2. React...
Scheme 4: Isotope-labeling experiments.
Scheme 5: Proposed reaction mechanism for the Rh-catalyzed reductive carbonylation of aryl iodides using CO a...
Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35
Graphical Abstract
Scheme 1: Synthesis of pyridylphosphine ligands.
Figure 1: Pyridylphosphine ligands.
Scheme 2: Synthesis of piperidyl- and oxazinylphosphine ligands.
Scheme 3: Synthesis of linear multi-chelate pyridylphosphine ligands.
Scheme 4: Synthesis of chiral acetal pyridylphosphine ligands.
Scheme 5: Synthesis of diphenylphosphine-substituted triazine ligands.
Scheme 6: Synthesis of (pyridine-2-ylmethyl)phosphine ligands.
Scheme 7: Synthesis of diphosphine pyrrole ligands.
Scheme 8: Synthesis of 4,5-diazafluorenylphosphine ligands.
Scheme 9: Synthesis of thioether-containing pyridyldiphosphine ligands starting from ethylene sulfide and dip...
Scheme 10: Synthesis of monoterpene-derived phosphine pyridine ligands.
Scheme 11: Synthesis of N-phenylphosphine-substituted imidazole ligands.
Scheme 12: Synthesis of triazol-4-ylphosphine ligands.
Scheme 13: Synthesis of phosphanyltriazolopyridines and product selectivity depending on the substituents’ eff...
Scheme 14: Synthesis of PTA-phosphine ligands.
Scheme 15: Synthesis of isomeric phosphine dipyrazole ligands by varying the reaction temperature.
Scheme 16: Synthesis of N-tethered phosphine imidazolium ligands (route A) and diphosphine imidazolium ligands...
Scheme 17: Synthesis of {1-[2-(pyridin-2-yl)- (R = CH) and {1-[2-(pyrazin-2-yl)quinazolin-4-yl]naphthalen-2-yl...
Scheme 18: Synthesis of oxazolylindolylphosphine ligands 102.
Scheme 19: Synthesis of pyrrolylphosphine ligands.
Scheme 20: Synthesis of phosphine guanidinium ligands.
Scheme 21: Synthesis of a polydentate aminophosphine ligand.
Scheme 22: Synthesis of quinolylphosphine ligands.
Scheme 23: Synthesis of N-(triazolylmethyl)phosphanamine ligands.
Figure 2: Triazolylphosphanamine ligands synthesized by Wassenaar’s method [22].
Scheme 24: Synthesis of oxazaphosphorines.
Scheme 25: Synthesis of paracyclophane pyridylphosphine ligands.
Scheme 26: Synthesis of triazolylphosphine ligands.
Figure 3: Click-phosphine ligands.
Scheme 27: Ferrocenyl pyridylphosphine imine ligands.
Scheme 28: Synthesis of phosphinooxazolines (PHOX).
Scheme 29: Synthesis of ferrocenylphosphine oxazoles.
Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218
Graphical Abstract
Scheme 1: The main three strategies of fluorination: nucleophilic, electrophilic and radical fluorination.
Scheme 2: Doyle’s Pd-catalyzed fluorination of allylic chlorides.
Scheme 3: Allylic fluorination of 2- and 3-substituted propenyl esters.
Scheme 4: Regioselective allylic fluorination of cinnamyl phosphorothioate esters.
Scheme 5: Palladium-catalyzed aliphatic C–H fluorination reported by Doyle.
Scheme 6: Pd-catalyzed enantioselective fluorination of α-ketoesters followed by stereoselective reduction to...
Scheme 7: Pd-catalyzed C(sp3)–H fluorination of oxindoles.
Scheme 8: C–H fluorination of 8-methylquinoline derivatives with F− reagents.
Scheme 9: Fluorination of α-cyano acetates reported by van Leeuwen.
Scheme 10: The catalytic enantioselective electrophilic C–H fluorination of α-chloro-β-keto phosphonates.
Scheme 11: Fluorination of unactivated C(sp3)–H bonds directed by the bidentate PIP auxiliary.
Scheme 12: Fluorination of C(sp3)–H bonds at the β-position of carboxylic acids.
Scheme 13: Enantioselective benzylic C–H fluorination with a chiral transient directing group.
Scheme 14: Microwave-heated Pd-catalyzed fluorination of aryl alcohols.
Scheme 15: Fluorination of aryl potassium trifluoroborates.
Scheme 16: C(sp2)–F bond formation using precatalyst [L·Pd]2(cod).
Scheme 17: Pd-catalyzed fluorination of (hetero)aryl triflates and bromides.
Scheme 18: The Pd-catalyzed C–H fluorination of arenes with Selectfluor/NFSI.
Scheme 19: Pd(II)-catalyzed ortho-monofluorination protocol for benzoic acids.
Scheme 20: Pd-catalyzed C(sp2)–H bond fluorination of 2-arylbenzothiazoles.
Scheme 21: Nitrate-promoted fluorination of aromatic and olefinic C(sp2)–H bonds and proposed mechanism.
Scheme 22: Fluorination of oxalyl amide-protected benzylamine derivatives.
Scheme 23: C–H fluorination of benzaldehydes with orthanilic acids as transient directing group.
Scheme 24: Pd(II)-catalyzed aryl C–H fluorination with various directing groups.
Scheme 25: Cu-catalyzed aliphatic, allylic, and benzylic fluorination.
Scheme 26: Cu-catalyzed SN2 fluorination of primary and secondary alkyl bromides.
Scheme 27: Copper-catalyzed fluorination of alkyl triflates.
Scheme 28: Cu-catalyzed fluorination of allylic bromides and chlorides.
Scheme 29: Synthetic strategy for the fluorination of active methylene compounds.
Scheme 30: Fluorination of β-ketoesters using a tartrate-derived bidentate bisoxazoline-Cu(II) complex.
Scheme 31: Highly enantioselective fluorination of β-ketoesters and N-Boc-oxindoles.
Scheme 32: Amide group-assisted site-selective fluorination of α-bromocarbonyl compounds.
Scheme 33: Cu-mediated aryl fluorination reported by Sanford [77].
Scheme 34: Mono- or difluorination reactions of benzoic acid derivatives.
Scheme 35: Cu-catalyzed fluorination of diaryliodonium salts with KF.
Scheme 36: Copper(I)-catalyzed cross-coupling of 2-pyridylaryl bromides.
Scheme 37: AgNO3-catalyzed decarboxylative fluorination of aliphatic carboxylic acids.
Scheme 38: The Mn-catalyzed aliphatic and benzylic C–H fluorination.
Scheme 39: Iron(II)-promoted C–H fluorination of benzylic substrates.
Scheme 40: Ag-catalyzed fluorodecarboxylation of carboxylic acids.
Scheme 41: Vanadium-catalyzed C(sp3)–H fluorination.
Scheme 42: AgNO3-catalyzed radical deboronofluorination of alkylboronates and boronic acids.
Scheme 43: Selective heterobenzylic C–H fluorination with Selectfluor reported by Van Humbeck.
Scheme 44: Fe(II)-catalyzed site-selective fluorination guided by an alkoxyl radical.
Scheme 45: Fluorination of allylic trichloroacetimidates reported by Nguyen et al.
Scheme 46: Iridium-catalyzed fluorination of allylic carbonates with TBAF(t-BuOH)4.
Scheme 47: Iridium-catalyzed asymmetric fluorination of allylic trichloroacetimidates.
Scheme 48: Cobalt-catalyzed α-fluorination of β-ketoesters.
Scheme 49: Nickel-catalyzed α-fluorination of various α-chloro-β-ketoesters.
Scheme 50: Ni(II)-catalyzed enantioselective fluorination of oxindoles and β-ketoesters.
Scheme 51: Scandium(III)-catalyzed asymmetric C–H fluorination of unprotected 3-substituted oxindoles.
Scheme 52: Iron-catalyzed directed C–H fluorination.
Scheme 53: Electrophilic silver-catalyzed Ar–F bond-forming reaction from arylstannanes.
Figure 1: Nucleophilic, electrophilic and radical CF3 sources.
Scheme 54: Cu(I)-catalyzed allylic trifluoromethylation of unactivated terminal olefins.
Scheme 55: Direct copper-catalyzed trifluoromethylation of allylsilanes.
Scheme 56: Cupper-catalyzed enantioselective trifluoromethylation of five and six-membered ring β-ketoesters.
Scheme 57: Cu-catalyzed highly stereoselective trifluoromethylation of secondary propargyl sulfonates.
Scheme 58: Remote C(sp3)–H trifluoromethylation of carboxamides and sulfonamides.
Scheme 59: Trifluoromethylation of allylsilanes with photoredox catalysis.
Scheme 60: Ag-catalyzed decarboxylative trifluoromethylation of aliphatic carboxylic acids in aqueous CH3CN.
Scheme 61: Decarboxylative trifluoromethylation of aliphatic carboxylic acids via combined photoredox and copp...
Scheme 62: Palladium-catalyzed Ar–CF3 bond-forming reaction.
Scheme 63: Palladium-catalyzed trifluoromethylation of arenes with diverse heterocyclic directing groups.
Scheme 64: Pd-catalyzed trifluoromethylation of indoles as reported by Liu.
Scheme 65: Pd-catalyzed trifluoromethylation of vinyl triflates and vinyl nonaflates.
Scheme 66: Pd(II)-catalyzed ortho-trifluoromethylation of aromatic C–H bonds.
Scheme 67: Visible-light-induced Pd(OAc)2-catalyzed ortho-trifluoromethylation of acetanilides with CF3SO2Na.
Scheme 68: CuI-catalyzed trifluoromethylation of aryl- and alkenylboronic acids.
Scheme 69: Cu-catalyzed trifluoromethylation of aryl- and vinylboronic acids.
Scheme 70: Copper-catalyzed trifluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 71: Formation of C(sp2)–CF3 bond catalyzed by copper(I) complex.
Scheme 72: Loh’s Cu(I)-catalyzed trifluoromethylation of enamides and electron-deficient alkenes.
Scheme 73: Copper and iron-catalyzed decarboxylative tri- and difluoromethylation.
Scheme 74: Cu-catalyzed trifluoromethylation of hydrazones developed by Bouyssi.
Scheme 75: Cu(I)-catalyzed trifluoromethylation of terminal alkenes.
Scheme 76: Cu/Ag-catalyzed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 77: Copper-catalyzed direct alkenyl C–H trifluoromethylation.
Scheme 78: Copper(I/II)-catalyzed direct trifluoromethylation of styrene derivatives.
Scheme 79: Regioselective trifluoromethylation of pivalamido arenes and heteroarenes.
Scheme 80: Synthesis of trifluoromethylquinones in the presence of copper(I).
Scheme 81: Oxidative trifluoromethylation of imidazoheterocycles in ionic liquid/water.
Scheme 82: A mild and fast continuous-flow trifluoromethylation of coumarins using a CuI/CF3SO2Na/TBHP system.
Scheme 83: Copper-catalyzed oxidative trifluoromethylation of various 8-aminoquinolines.
Scheme 84: PA-directed copper-catalyzed trifluoromethylation of anilines.
Scheme 85: Trifluoromethylation of potassium vinyltrifluoroborates catalyzed by Fe(II).
Scheme 86: Alkenyl trifluoromethylation catalyzed by Ru(phen)3Cl2 as photocatalyst.
Scheme 87: Ru-catalyzed trifluoromethylation of alkenes by Akita’s group.
Scheme 88: Ir-catalyzed Cvinyl–CF3 bond formation of α,β-unsaturated carboxylic acids.
Scheme 89: Ag(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes.
Scheme 90: Photocatalyzed direct trifluoromethylation of aryl and heteroaryl C–H bonds.
Scheme 91: Rhenium (MTO)-catalyzed direct trifluoromethylation of aromatic substrates.
Scheme 92: Trifluoromethylation of unprotected anilines under [Ir(ppy)3] catalyst.
Scheme 93: Oxidative trifluoromethylation of imidazopyridines and imidazoheterocycles.
Scheme 94: Ruthenium-catalyzed trifluoromethylation of (hetero)arenes with trifluoroacetic anhydride.
Scheme 95: Phosphovanadomolybdic acid-catalyzed direct C–H trifluoromethylation.
Scheme 96: Picolinamide-assisted ortho-trifluoromethylation of arylamines.
Scheme 97: A nickel-catalyzed C–H trifluoromethylation of free anilines.
Scheme 98: Cu-mediated trifluoromethylation of terminal alkynes reported by Qing.
Scheme 99: Huang’s C(sp)–H trifluoromethylation using Togni’s reagent.
Scheme 100: Cu-catalyzed methods for trifluoromethylation with Umemoto’s reagent.
Scheme 101: The synthesis of alkynyl-CF3 compounds in the presence of fac-[Ir(ppy)3] under visible-light irradi...
Scheme 102: Pd-catalyzed Heck reaction reported by Reutrakul.
Scheme 103: Difluoromethylation of enamides and ene-carbamates.
Scheme 104: Difluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 105: Copper-catalyzed direct C(sp2)–H difluoroacetylation reported by Pannecoucke and co-workers.
Scheme 106: Difluoroalkylation of aldehyde-derived hydrazones with functionalized difluoromethyl bromides.
Scheme 107: Photoredox-catalyzed C–H difluoroalkylation of aldehyde-derived hydrazones.
Scheme 108: Synergistic ruthenium(II)-catalyzed C–H difluoromethylation reported by Ackermann.
Scheme 109: Visible-light photocatalytic decarboxylation of α,β-unsaturated carboxylic acids.
Scheme 110: Synthesis of difluorinated ketones via S-alkyl dithiocarbamates obtained from acyl chlorides and po...
Scheme 111: Synthesis of aryl and heteroaryl difluoromethylated phosphonates.
Scheme 112: Difluoroalkylation of secondary propargyl sulfonates using Cu as the catalyst.
Scheme 113: Ru(II)-mediated para-selective difluoromethylation of anilides and their derivatives.
Scheme 114: Bulky diamine ligand promoted cross-coupling of difluoroalkyl bromides.
Scheme 115: Copper-catalyzed C3–H difluoroacetylation of quinoxalinones.
Scheme 116: Copper(I) chloride-catalyzed trifluoromethylthiolation of enamines, indoles and β-ketoesters.
Scheme 117: Copper-boxmi-catalyzed asymmetric trifluoromethylthiolation of β-ketoesters.
Scheme 118: Direct Cu-catalyzed trifluoromethylthiolation of boronic acids and alkynes.
Scheme 119: Cu-catalyzed synthesis of α-trifluoromethylthio-substituted ketones.
Scheme 120: Trifluoromethylthiolation reactions promoted by diazotriflone and copper.
Scheme 121: Halide activation of N-(trifluoromethylthio)phthalimide.
Scheme 122: The visible light-promoted trifluoromethylthiolation reported by Glorius.
Scheme 123: Synthesis of α-trifluoromethylthioesters via Goossen’s approach.
Scheme 124: Photoinduced trifluoromethylthiolation of diazonium salts.
Scheme 125: Ag-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids.
Scheme 126: Catalytic (hetero)aryl C–H trifluoromethoxylation under visible light.
Scheme 127: Photoinduced C–H-bond trifluromethoxylation of (hetero)arenes.
Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165
Graphical Abstract
Figure 1: Various drugs having IP nucleus.
Figure 2: Participation percentage of various TMs for the syntheses of IPs.
Scheme 1: CuI–NaHSO4·SiO2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 2: Experimental examination of reaction conditions.
Scheme 3: One-pot tandem reaction for the synthesis of 2-haloimidazopyridines.
Scheme 4: Mechanistic scheme for the synthesis of 2-haloimidazopyridine.
Scheme 5: Copper-MOF-catalyzed three-component reaction (3-CR) for imidazo[1,2-a]pyridines.
Scheme 6: Mechanism for copper-MOF-driven synthesis.
Scheme 7: Heterogeneous synthesis via titania-supported CuCl2.
Scheme 8: Mechanism involving oxidative C–H functionalization.
Scheme 9: Heterogeneous synthesis of IPs.
Scheme 10: One-pot regiospecific synthesis of imidazo[1,2-a]pyridines.
Scheme 11: Vinyl azide as an unprecedented substrate for imidazo[1,2-a]pyridines.
Scheme 12: Radical pathway.
Scheme 13: Cu(I)-catalyzed transannulation approach for imidazo[1,5-a]pyridines.
Scheme 14: Plausible radical pathway for the synthesis of imidazo[1,5-a]pyridines.
Scheme 15: A solvent-free domino reaction for imidazo[1,2-a]pyridines.
Scheme 16: Cu-NPs-mediated synthesis of imidazo[1,2-a]pyridines.
Scheme 17: CuI-catalyzed synthesis of isoxazolylimidazo[1,2-a]pyridines.
Scheme 18: Functionalization of 4-bromo derivative via Sonogashira coupling reaction.
Scheme 19: A plausible reaction pathway.
Scheme 20: Cu(I)-catalyzed intramolecular oxidative C–H amidation reaction.
Scheme 21: One-pot synthetic reaction for imidazo[1,2-a]pyridine.
Scheme 22: Plausible reaction mechanism.
Scheme 23: Cu(OAc)2-promoted synthesis of imidazo[1,2-a]pyridines.
Scheme 24: Mechanism for aminomethylation/cycloisomerization of propiolates with imines.
Scheme 25: Three-component synthesis of imidazo[1,2-a]pyridines.
Figure 3: Scope of pyridin-2(1H)-ones and acetophenones.
Scheme 26: CuO NPS-promoted A3 coupling reaction.
Scheme 27: Cu(II)-catalyzed C–N bond formation reaction.
Scheme 28: Mechanism involving Chan–Lam/Ullmann coupling.
Scheme 29: Synthesis of formyl-substituted imidazo[1,2-a]pyridines.
Scheme 30: A tandem sp3 C–H amination reaction.
Scheme 31: Probable mechanistic approach.
Scheme 32: Dual catalytic system for imidazo[1,2-a]pyridines.
Scheme 33: Tentative mechanism.
Scheme 34: CuO/CuAl2O4/ᴅ-glucose-promoted 3-CCR.
Scheme 35: A tandem CuOx/OMS-2-based synthetic strategy.
Figure 4: Biomimetic catalytic oxidation in the presence of electron-transfer mediators (ETMs).
Scheme 36: Control experiment.
Scheme 37: Copper-catalyzed C(sp3)–H aminatin reaction.
Scheme 38: Reaction of secondary amines.
Scheme 39: Probable mechanistic pathway.
Scheme 40: Coupling reaction of α-azidoketones.
Scheme 41: Probable pathway.
Scheme 42: Probable mechanism with free energy calculations.
Scheme 43: MCR for cyanated IP synthesis.
Scheme 44: Substrate scope for the reaction.
Scheme 45: Reaction mechanism.
Scheme 46: Probable mechanistic pathway for Cu/ZnAl2O4-catalyzed reaction.
Scheme 47: Copper-catalyzed double oxidative C–H amination reaction.
Scheme 48: Application towards different coupling reactions.
Scheme 49: Reaction mechanism.
Scheme 50: Condensation–cyclization approach for the synthesis of 1,3-diarylated imidazo[1,5-a]pyridines.
Scheme 51: Optimized reaction conditions.
Scheme 52: One-pot 2-CR.
Scheme 53: One-pot 3-CR without the isolation of chalcone.
Scheme 54: Copper–Pybox-catalyzed cyclization reaction.
Scheme 55: Mechanistic pathway catalyzed by Cu–Pybox complex.
Scheme 56: Cu(II)-promoted C(sp3)-H amination reaction.
Scheme 57: Wider substrate applicability for the reaction.
Scheme 58: Plausible reaction mechanism.
Scheme 59: CuI assisted C–N cross-coupling reaction.
Scheme 60: Probable reaction mechanism involving sp3 C–H amination.
Scheme 61: One-pot MCR-catalyzed by CoFe2O4/CNT-Cu.
Scheme 62: Mechanistic pathway.
Scheme 63: Synthetic scheme for 3-nitroimidazo[1,2-a]pyridines.
Scheme 64: Plausible mechanism for CuBr-catalyzed reaction.
Scheme 65: Regioselective synthesis of halo-substituted imidazo[1,2-a]pyridines.
Scheme 66: Synthesis of 2-phenylimidazo[1,2-a]pyridines.
Scheme 67: Synthesis of diarylated compounds.
Scheme 68: CuBr2-mediated one-pot two-component oxidative coupling reaction.
Scheme 69: Decarboxylative cyclization route to synthesize 1,3-diarylimidazo[1,5-a]pyridines.
Scheme 70: Mechanistic pathway.
Scheme 71: C–H functionalization reaction of enamines to produce diversified heterocycles.
Scheme 72: A plausible mechanism.
Scheme 73: CuI-promoted aerobic oxidative cyclization reaction of ketoxime acetates and pyridines.
Scheme 74: CuI-catalyzed pathway for the formation of imidazo[1,2-a]pyridine.
Scheme 75: Mechanistic pathway.
Scheme 76: Mechanistic rationale for the synthesis of products.
Scheme 77: Copper-catalyzed synthesis of vinyloxy-IP.
Scheme 78: Regioselective product formation with propiolates.
Scheme 79: Proposed mechanism for vinyloxy-IP formation.
Scheme 80: Regioselective synthesis of 3-hetero-substituted imidazo[1,2-a]pyridines with different reaction su...
Scheme 81: Mechanistic pathway.
Scheme 82: CuI-mediated synthesis of 3-formylimidazo[1,2-a]pyridines.
Scheme 83: Radical pathway for 3-formylated IP synthesis.
Scheme 84: Pd-catalyzed urea-cyclization reaction for IPs.
Scheme 85: Pd-catalyzed one-pot-tandem amination and intramolecular amidation reaction.
Figure 5: Scope of aniline nucleophiles.
Scheme 86: Pd–Cu-catalyzed Sonogashira coupling reaction.
Scheme 87: One-pot amide coupling reaction for the synthesis of imidazo[4,5-b]pyridines.
Scheme 88: Urea cyclization reaction for the synthesis of two series of pyridines.
Scheme 89: Amidation reaction for the synthesis of imidazo[4,5-b]pyridines.
Figure 6: Amide scope.
Scheme 90: Pd NPs-catalyzed 3-component reaction for the synthesis of 2,3-diarylated IPs.
Scheme 91: Plausible mechanistic pathway for Pd NPs-catalyzed MCR.
Scheme 92: Synthesis of chromenoannulated imidazo[1,2-a]pyridines.
Scheme 93: Mechanism for the synthesis of chromeno-annulated IPs.
Scheme 94: Zinc oxide NRs-catalyzed synthesis of imidazo[1,2-a]azines/diazines.
Scheme 95: Zinc oxide-catalyzed isocyanide based GBB reaction.
Scheme 96: Reaction pathway for ZnO-catalyzed GBB reaction.
Scheme 97: Mechanistic pathway.
Scheme 98: ZnO NRs-catalyzed MCR for the synthesis of imidazo[1,2-a]azines.
Scheme 99: Ugi type GBB three-component reaction.
Scheme 100: Magnetic NPs-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 101: Regioselective synthesis of 2-alkoxyimidazo[1,2-a]pyridines catalyzed by Fe-SBA-15.
Scheme 102: Plausible mechanistic pathway for the synthesis of 2-alkoxyimidazopyridine.
Scheme 103: Iron-catalyzed synthetic approach.
Scheme 104: Iron-catalyzed aminooxygenation reaction.
Scheme 105: Mechanistic pathway.
Scheme 106: Rh(III)-catalyzed double C–H activation of 2-substituted imidazoles and alkynes.
Scheme 107: Plausible reaction mechanism.
Scheme 108: Rh(III)-catalyzed non-aromatic C(sp2)–H bond activation–functionalization for the synthesis of imid...
Scheme 109: Reactivity and selectivity of different substrates.
Scheme 110: Rh-catalyzed direct C–H alkynylation by Li et al.
Scheme 111: Suggested radical mechanism.
Scheme 112: Scandium(III)triflate-catalyzed one-pot reaction and its mechanism for the synthesis of benzimidazo...
Scheme 113: RuCl3-assisted Ugi-type Groebke–Blackburn condensation reaction.
Scheme 114: C-3 aroylation via Ru-catalyzed two-component reaction.
Scheme 115: Regioselective synthetic mechanism.
Scheme 116: La(III)-catalyzed one-pot GBB reaction.
Scheme 117: Mechanistic approach for the synthesis of imidazo[1,2-a]pyridines.
Scheme 118: Synthesis of imidazo[1,2-a]pyridine using LaMnO3 NPs under neat conditions.
Scheme 119: Mechanistic approach.
Scheme 120: One-pot 3-CR for regioselective synthesis of 2-alkoxy-3-arylimidazo[1,2-a]pyridines.
Scheme 121: Formation of two possible products under optimization of the catalysts.
Scheme 122: Mechanistic strategy for NiFe2O4-catalyzed reaction.
Scheme 123: Two-component reaction for synthesizing imidazodipyridiniums.
Scheme 124: Mechanistic scheme for the synthesis of imidazodipyridiniums.
Scheme 125: CuI-catalyzed arylation of imidazo[1,2-a]pyridines.
Scheme 126: Mechanism for arylation reaction.
Scheme 127: Cupric acetate-catalyzed double carbonylation approach.
Scheme 128: Radical mechanism for double carbonylation of IP.
Scheme 129: C–S bond formation reaction catalyzed by cupric acetate.
Scheme 130: Cupric acetate-catalyzed C-3 formylation approach.
Scheme 131: Control experiments for signifying the role of DMSO and oxygen.
Scheme 132: Mechanism pathway.
Scheme 133: Copper bromide-catalyzed CDC reaction.
Scheme 134: Extension of the substrate scope.
Scheme 135: Plausible radical pathway.
Scheme 136: Transannulation reaction for the synthesis of imidazo[1,5-a]pyridines.
Scheme 137: Plausible reaction pathway for denitrogenative transannulation.
Scheme 138: Cupric acetate-catalyzed C-3 carbonylation reaction.
Scheme 139: Plausible mechanism for regioselective C-3 carbonylation.
Scheme 140: Alkynylation reaction at C-2 of 3H-imidazo[4,5-b]pyridines.
Scheme 141: Two-way mechanism for C-2 alkynylation of 3H-imidazo[4,5-b]pyridines.
Scheme 142: Palladium-catalyzed SCCR approach.
Scheme 143: Palladium-catalyzed Suzuki coupling reaction.
Scheme 144: Reaction mechanism.
Scheme 145: A phosphine free palladium-catalyzed synthesis of C-3 arylated imidazopyridines.
Scheme 146: Palladium-mediated Buchwald–Hartwig cross-coupling reaction.
Figure 7: Structure of the ligands optimized.
Scheme 147: Palladium acetate-catalyzed direct arylation of imidazo[1,2-a]pyridines.
Scheme 148: Palladium acetate-catalyzed mechanistic pathway.
Scheme 149: Palladium acetate-catalyzed regioselective arylation reported by Liu and Zhan.
Scheme 150: Mechanism for selective C-3 arylation of IP.
Scheme 151: Pd(II)-catalyzed alkenylation reaction with styrenes.
Scheme 152: Pd(II)-catalyzed alkenylation reaction with acrylates.
Scheme 153: A two way mechanism.
Scheme 154: Double C–H activation reaction catalyzed by Pd(OAc)2.
Scheme 155: Probable mechanism.
Scheme 156: Palladium-catalyzed decarboxylative coupling.
Scheme 157: Mechanistic cycle for decarboxylative arylation reaction.
Scheme 158: Ligand-free approach for arylation of imidazo[1,2-a]pyridine-3-carboxylic acids.
Scheme 159: Mechanism for ligandless arylation reaction.
Scheme 160: NHC-Pd(II) complex assisted arylation reaction.
Scheme 161: C-3 arylation of imidazo[1,2-a]pyridines with aryl bromides catalyzed by Pd(OAc)2.
Scheme 162: Pd(II)-catalyzed C-3 arylations with aryl tosylates and mesylates.
Scheme 163: CDC reaction for the synthesis of imidazo[1,2-a]pyridines.
Scheme 164: Plausible reaction mechanism for Pd(OAc)2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 165: Pd-catalyzed C–H amination reaction.
Scheme 166: Mechanism for C–H amination reaction.
Scheme 167: One-pot synthesis for 3,6-di- or 2,3,6-tri(hetero)arylimidazo[1,2-a]pyridines.
Scheme 168: C–H/C–H cross-coupling reaction of IPs and azoles catalyzed by Pd(II).
Scheme 169: Mechanistic cycle.
Scheme 170: Rh-catalyzed C–H arylation reaction.
Scheme 171: Mechanistic pathway for C–H arylation of imidazo[1,2-a]pyridine.
Scheme 172: Rh(III)-catalyzed double C–H activation of 2-phenylimidazo[1,2-a]pyridines and alkynes.
Scheme 173: Rh(III)-catalyzed mechanistic pathway.
Scheme 174: Rh(III)-mediated oxidative coupling reaction.
Scheme 175: Reactions showing functionalization of the product obtained by the group of Kotla.
Scheme 176: Mechanism for Rh(III)-catalyzed oxidative coupling reaction.
Scheme 177: Rh(III)-catalyzed C–H activation reaction.
Scheme 178: Mechanistic cycle.
Scheme 179: Annulation reactions of 2-arylimidazo[1,2-a]pyridines and alkynes.
Scheme 180: Two-way reaction mechanism for annulations reaction.
Scheme 181: [RuCl2(p-cymene)]2-catalyzed C–C bond formation reaction.
Scheme 182: Reported reaction mechanism.
Scheme 183: Fe(III) catalyzed C-3 formylation approach.
Scheme 184: SET mechanism-catalyzed by Fe(III).
Scheme 185: Ni(dpp)Cl2-catalyzed KTC coupling.
Scheme 186: Pd-catalyzed SM coupling.
Scheme 187: Vanadium-catalyzed coupling of IP and NMO.
Scheme 188: Mechanistic cycle.
Scheme 189: Selective C3/C5–H bond functionalizations by mono and bimetallic systems.
Scheme 190: rGO-Ni@Pd-catalyzed C–H bond arylation of imidazo[1,2-a]pyridine.
Scheme 191: Mechanistic pathway for heterogeneously catalyzed arylation reaction.
Scheme 192: Zinc triflate-catalyzed coupling reaction of substituted propargyl alcohols.
Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39
Graphical Abstract
Scheme 1: Most common metathesis reactions. Ring-opening metathesis polymerization (ROMP), acyclic diene meta...
Scheme 2: Catalytic cycle for metathesis proposed by Chauvin.
Figure 1: Some of the most representative catalysts for aqueous metathesis. a) Well-defined ruthenium catalys...
Scheme 3: First aqueous ROMP reactions catalyzed by ruthenium(III) salts.
Scheme 4: Degradation pathway of first generation Grubbs catalyst (G-I) in methanol.
Scheme 5: Synthesis of Blechert-type catalysts 19 and 20.
Figure 2: Chemical structure and components of amphiphilic molecule PTS and derivatives.
Scheme 6: RCM of selected substrates in the presence of the surfactant PTS. Conditionsa: The reaction was car...
Scheme 7: RCM reactions of substrates 31 and 33 with the encapsulated G-II catalyst.
Scheme 8: Living ROMP of norbornene derivatives 35 and 36 with phosphine-based catalysts bearing quaternary a...
Scheme 9: Synthesis of water-soluble catalysts 3 and 4 bearing quaternary ammonium tags.
Scheme 10: In situ formation of catalyst 5 bearing a quaternary ammonium group.
Scheme 11: Catalyst recycling of an ammonium-bearing catalyst.
Scheme 12: Removal of the water-soluble catalyst 12 through host–guest interaction with silica-gel-supported β...
Scheme 13: Selection of artificial metathases reported by Ward and co-workers (ArM 1 based on biotin–(strept)a...
Figure 3: In vivo metathesis with an artificial metalloenzyme based on the biotin–streptavidin technology.
Scheme 14: Artificial metathase based on covalent anchoring approach. α-Chymotrypsin interacts with catalyst 66...
Scheme 15: Assembling an artificial metathase (ArM 4) based on the small heat shock protein from M. Jannaschii...
Scheme 16: Artificial metathases based on cavity-size engineered β-barrel protein nitrobindin (NB4exp). The HG...
Scheme 17: Artificial metathase based on cutinase (ArM 8) and resulting metathesis activities.
Scheme 18: Site-specific modification of proteins via aqueous cross-metathesis. The protein structure is based...
Scheme 19: a) Allyl homocysteine (Ahc)-modified proteins as CM substrates. b) Incorporation of Ahc in the Fc p...
Scheme 20: On-DNA cross-metathesis reaction of allyl sulfide 99.
Scheme 21: Preparation of BODIPY-containing profluorescent probes 102 and 104.
Scheme 22: Metathesis-based ethylene detection in live cells.
Scheme 23: First example of stapled peptides via olefin metathesis.
Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266
Graphical Abstract
Scheme 1: NHC’s and their ruthenium complexes studied in this work; L = carbene 1, 2 or 3.
Scheme 2: Schematic representation of carbene dimerization and atom numbering scheme used throughout this wor...
Scheme 3: Dissociative mechanism of initiation for Grubbs-like 1–3-GrI and M1 indenylidene type complexes 1–3...
Scheme 4: Dissociative mechanism of initiation of 2nd generation Grubbs-like saturated 1–3-GrII and unsaturat...
Scheme 5: Dissociative mechanism of activation for complexes 1–3-Hov; L = carbene 1, 2 or 3.
Beilstein J. Org. Chem. 2018, 14, 2730–2736, doi:10.3762/bjoc.14.251
Graphical Abstract
Figure 1: Alcohol→bromide functional group transformations.
Figure 2: Ligands used in the library generation of heteroleptic copper(I)-based complexes for photocatalysis....
Figure 3: Evaluation of the library of copper-based complexes in photocatalytic alcohol→bromide conversion. R...
Figure 4: Experimental set-up for the photocatalytic conversion of alcohols to bromides. PFA tubing is wrappe...
Scheme 1: Copper-based photocatalysis for photocatalytic synthesis of an anhydride.
Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128
Graphical Abstract
Scheme 1: Strategies to address the issue of sustainability with polyvalent organoiodine reagents.
Scheme 2: Functionalization of ketones and alkenes with IBX.
Scheme 3: Functionalization of pyrroles with DMP.
Scheme 4: Catalytic benzoyloxy-trifluoromethylation reported by Szabó.
Scheme 5: Catalytic benzoyloxy-trifluoromethylation reported by Mideoka.
Scheme 6: Catalytic 1,4-benzoyloxy-trifluoromethylation of dienes.
Scheme 7: Catalytic benzoyloxy-trifluoromethylation of allylamines.
Scheme 8: Catalytic benzoyloxy-trifluoromethylation of enynes.
Scheme 9: Catalytic benzoyloxy-trifluoromethylation of allenes.
Scheme 10: Alkynylation of N-(aryl)imines with EBX for the formation of furans.
Scheme 11: Catalytic benzoyloxy-alkynylation of diazo compounds.
Scheme 12: Catalytic asymmetric benzoyloxy-alkynylation of diazo compounds.
Scheme 13: Catalytic 1,2-benzoyloxy-azidation of alkenes.
Scheme 14: Catalytic 1,2-benzoyloxy-azidation of enamides.
Scheme 15: Catalytic 1,2-benzoyloxy-iodination of alkenes.
Scheme 16: Seminal study with cyclic diaryl-λ3-iodane.
Scheme 17: Synthesis of alkylidenefluorenes from cyclic diaryl-λ3-iodanes.
Scheme 18: Synthesis of alkyne-substituted alkylidenefluorenes.
Scheme 19: Synthesis of phenanthrenes from cyclic diaryl-λ3-iodanes.
Scheme 20: Synthesis of dibenzocarbazoles from cyclic diaryl-λ3-iodanes.
Scheme 21: Synthesis of triazolophenantridines from cyclic diaryl-λ3-iodanes.
Scheme 22: Synthesis of functionalized benzoxazoles from cyclic diaryl-λ3-iodanes.
Scheme 23: Sequential difunctionalization of cyclic diaryl-λ3-iodanes.
Scheme 24: Double Suzuki–Miyaura coupling reaction of cyclic diaryl-λ3-iodanes.
Scheme 25: Synthesis of a δ-carboline from cyclic diaryl-λ3-iodane.
Scheme 26: Synthesis of N-(aryl)carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 27: Synthesis of carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 28: Synthesis of carbazoles and acridines from cyclic diaryl-λ3-iodanes.
Scheme 29: Synthesis of dibenzothiophenes from cyclic diaryl-λ3-iodanes.
Scheme 30: Synthesis of various sulfur heterocycles from cyclic diaryl-λ3-iodanes.
Scheme 31: Synthesis of dibenzothioheterocycles from cyclic diaryl-λ3-iodanes.
Scheme 32: Synthesis of dibenzosulfides and dibenzoselenides from cyclic diaryl-λ3-iodanes.
Scheme 33: Synthesis of dibenzosulfones from cyclic diaryl-λ3-iodanes.
Scheme 34: Seminal study with linear diaryl-λ3-iodanes.
Scheme 35: N-Arylation of benzotriazole with symmetrical diaryl-λ3-iodanes.
Scheme 36: Tandem catalytic C–H/N–H arylation of indoles with diaryl-λ3-iodanes.
Scheme 37: Tandem N-arylation/C(sp2)–H arylation with diaryl-λ3-iodanes.
Scheme 38: Catalytic intermolecular diarylation of anilines with diaryl-λ3-iodanes.
Scheme 39: Catalytic synthesis of diarylsulfides with diaryl-λ3-iodanes.
Scheme 40: α-Arylation of enolates using [bis(trifluoroacetoxy)iodo]arenes.
Scheme 41: Mechanism of the α-arylation using [bis(trifluoroacetoxy)iodo]arene.
Scheme 42: Catalytic nitrene additions mediated by [bis(acyloxy)iodo]arenes.
Scheme 43: Tandem of C(sp3)–H amination/sila-Sonogashira–Hagihara coupling.
Scheme 44: Tandem reaction using a λ3-iodane as an oxidant, a substrate and a coupling partner.
Scheme 45: Synthesis of 1,2-diarylated acrylamidines with ArI(OAc)2.
Beilstein J. Org. Chem. 2018, 14, 576–582, doi:10.3762/bjoc.14.44
Graphical Abstract
Scheme 1: Synthesis of chiral α-fluoroalkylated tertiary alcohols.
Scheme 2: Scope of fluoroalkylated pyruvates. Yields were determined by 19F NMR analysis using benzotrifluori...
Scheme 3: Catalytic asymmetric methylation of the simple perfluoroalkylated ketone 3a. Yields were determined...