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Search for "1,4-naphthoquinones" in Full Text gives 10 result(s) in Beilstein Journal of Organic Chemistry.
Trifluoromethylated hydrazones and acylhydrazones as potent nitrogen-containing fluorinated building blocks
- Zhang Dongxu
Beilstein J. Org. Chem. 2023, 19, 1741–1754, doi:10.3762/bjoc.19.127
- , 1,4-naphthoquinones, o-trimethylsilylphenyl triflate and chalcones have all been reacted with fluorinated nitrile imines to give a series of fluoroalkylated pyrazoles by Jasiński’s team [67][68][69][70][71][72] (Scheme 11a). Subsequently, Hu et al., Nie et al., and Ma et al. have all independently
Graphical Abstract
Scheme 1: Synthesis of trifluoromethylpyrazoles from trifluoroacetaldehyde hydrazones.
Scheme 2: Synthesis of polysubstituted pyrazolidines and pyrazolines.
Scheme 3: Asymmetric synthesis of 3-trifluoromethyl-1,4-dihydropyridazines reported by Rueping et al. [39].
Scheme 4: Synthesis of 3-trifluoromethyl-1,4-dihydropyridazine with Brønsted acid-assisted Lewis base catalys...
Scheme 5: Synthesis of CF3-pyrazoles and CF3-1,6-dihydropyridazines.
Scheme 6: Asymmetric reactions of trifluoromethylimines with organometallic reagents.
Scheme 7: Mannich-type reaction of trifluoroacetaldehyde hydrazones.
Scheme 8: Synthesis of trifluoromethylated hydrazonoyl halides.
Scheme 9: Early work of trifluoromethylated hydrazonoyl halides.
Scheme 10: [3 + 2]/[3 + 3] Cycloadditions of trifluoromethylated hydrazonoyl halides.
Scheme 11: Substrate scope for [3 + 2] cycloadditions with trifluoroacetonitrile imines reported by Jasiński’s...
Scheme 12: Synthesis of trifluoromethylated 1,2,4-triazole and 1,2,4-triazine derivatives.
Scheme 13: [3 + 2] Cycloadditions of difluoromethylated hydrazonoyl halides.
Scheme 14: Preparation and early applications of trifluoromethylated acylhydrazones.
Scheme 15: 1,2-Nucleophilic addition reactions of trifluoromethylated acylhydrazones.
Scheme 16: Cascade oxidation/cyclization reactions of trifluoromethylated homoallylic acylhydrazines.
Scheme 17: Synthesis of trifluoromethylated cyanohydrazines and 3-trifluoromethyl-1,2,4-triazolines.
Scheme 18: N-Arylation and N-alkylation of trifluoromethyl acylhydrazones.
Scheme 19: [3 + 2]-Cycladditions of trifluoromethyl acylhydrazones.
Menadione: a platform and a target to valuable compounds synthesis
- Acácio S. de Souza,
- Ruan Carlos B. Ribeiro,
- Dora C. S. Costa,
- Fernanda P. Pauli,
- David R. Pinho,
- Matheus G. de Moraes,
- Fernando de C. da Silva,
- Luana da S. M. Forezi and
- Vitor F. Ferreira
Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43
- isomers and trans-conformers. Menadione as a nucleophile Electron-rich 1,4-naphthoquinones, such as 2-hydroxy-, 2-amino-, and 2-alkylnaphtho-1,4-quinones may react as nucleophiles. Hence, menadione (10) can act as a nucleophile in, for example, bromination reactions [127] and aldol-type reactions with
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 Diels–Alder 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 Diels–Alder reaction for the synthesis of menadione (10).
Scheme 9: o-Toluidine as a dienophile in a Diels–Alder 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 Diels–Alder 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-ʟ-ascorbic acid under UV light irradiation.
Scheme 22: Selected approaches of menadione hydroacetylation to diacetylated menadiol.
Scheme 23: Thiele–Winter 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 Kochi–Anderson 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: Kochi–Anderson 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-Friedel–Crafts 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-González 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.
1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis
- Ruan Carlos B. Ribeiro,
- Patricia G. Ferreira,
- Amanda de A. Borges,
- Luana da S. M. Forezi,
- Fernando de Carvalho da Silva and
- Vitor F. Ferreira
Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5
- hydrocarbons (PAHs) [5][6]. Among all of the compounds in this class, 1,2- and 1,4-naphthoquinones stand out, as they are present in plants, fungi, lichens, bacteria, algae, viruses, insects, and higher organisms and perform several biochemical functions, such as defense, transference of electrons in various
Graphical Abstract
Figure 1: Naphthoquinones are commonly used in organic synthesis.
Figure 2: Some important natural and synthetic naphthoquinones.
Scheme 1: Synthetic studies of BNQs and reactions with amines.
Scheme 2: Methods described for the synthesis of β-NQS.
Figure 3: Drugs detected using β-NQSNa.
Scheme 3: Reactions between β-NQS and amines.
Scheme 4: Isomerization of 4-arylamino-1,2-naphthoquinones.
Scheme 5: Synthesis of unsymmetrical 2-amino-4-imino compounds.
Scheme 6: Synthesis of bis(isoxazolyl)naphthoquinones from β-NQS.
Scheme 7: The reaction of β-NQS with 30 followed by cycle condensation.
Scheme 8: Synthesis of 4-(2-amino-5-selenothiazoles)-1,2-naphthoquinones.
Scheme 9: Synthesis of amino- and phenoxy-1,2-naphthoquinones.
Scheme 10: Synthesis of 4-semicarbazide-1,2-naphthoquinone.
Scheme 11: Reactions of 4-azido-1,2-naphthoquinone.
Figure 4: Modifications that can be easily carried out from the products of β-NQS 8.
Scheme 12: Derivatives of 1,2-naphthoquinones obtained from β-NQS.
Scheme 13: Oximes as well as 4-amino- and 4-phenoxy-1,2-naphthoquinone as potential anti-inflammatory agents.
Scheme 14: Synthesis of triazoles from β-NQS.
Scheme 15: Synthesis of naphtho[1,2-d]oxazoles from β-NQS.
Scheme 16: A) Arylation and vinylation of β-NQS catalyzed by Ni(II) salts. B) Transformation of the 1,2-dicarb...
Scheme 17: Benzo[a]carbazole and benzo[c]carbazoles fused with 1,2-naphthoquinone.
Scheme 18: Synthesis of 1,2-naphthoquinones having a C=C bond from β-NQS. Method A: NaOH, EtOH/H2O, 40 °C, 2 h...
Scheme 19: C=C bond formation from β-NQS and substituted acetonitriles.
One hundred years of benzotropone chemistry
- Arif Dastan,
- Haydar Kilic and
- Nurullah Saracoglu
Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98
Graphical Abstract
Scheme 1: Tropone (1), tropolone (2) and their resonance structures.
Figure 1: Natural products containing a tropone nucleus.
Figure 2: Possible isomers 11–13 of benzotropone.
Scheme 2: Synthesis of benzotropones 11 and 12.
Scheme 3: Oxidation products of benzotropylium fluoroborate (16).
Scheme 4: Oxidation of 7-bromo-5H-benzo[7]annulene (22).
Scheme 5: Synthesis of 4,5-benzotropone (11) using o-phthalaldehyde (27).
Scheme 6: Synthesis of 4,5-benzotropone (11) starting from oxobenzonorbornadiene 31.
Scheme 7: Acid-catalyzed cleavage of oxo-bridge of 34.
Scheme 8: Synthesis of 4,5-benzotropone (11) from o-xylylene dibromide (38).
Scheme 9: Synthesis of 4,5-benzotropone (11) via the carbene adduct 41.
Scheme 10: Heck coupling strategy for the synthesis of 11.
Scheme 11: Synthesis of benzofulvalenes via carbonyl group of 4,5-benzotropone (11).
Figure 3: Some cycloheptatrienylium cations.
Scheme 12: Synthesis of condensation product 63 and its subsequent oxidative cyclization products.
Figure 4: A novel series of benzo[7]annulenes prepared from 4,5-benzotropone (11).
Scheme 13: Preparation of substituted benzo[7]annulene 72 using the Mukaiyama-Michael reaction.
Figure 5: Possible benzo[7]annulenylidenes 73–75.
Scheme 14: Thermal and photochemical decomposition of 7-diazo-7H-benzo[7]annulene (76) and the trapping of int...
Scheme 15: Synthesis of benzoheptafulvalene 86.
Scheme 16: Synthesis of 7-(diphenylmethylene)-7H-benzo[7]annulene (89).
Scheme 17: Reaction of 4,5-benzotropone (11) with dimethyl diazomethane.
Scheme 18: Synthesis of dihydrobenzomethoxyazocine 103.
Scheme 19: Synthesis and reducibility of benzo-homo-2-methoxyazocines.
Scheme 20: Synthesis of 4,5-benzohomotropones 104 and 115 from 4,5-benzotropones 11 and 113.
Scheme 21: A catalytic deuterogenation of 4,5-benzotropone (11) and synthesis of 5-monosubstituted benzo[7]ann...
Scheme 22: Synthesis of methyl benzo[7]annulenes 131 and 132.
Scheme 23: Ambident reactivity of halobenzo[7]annulenylium cations 133a/b.
Scheme 24: Preparation of benzo[7]annulenylidene–iron complexes 147.
Scheme 25: Synthesis of 1-ethynylbenzotropone (150) and the etheric compound 152 from 4,5-benzotropone (11) wi...
Scheme 26: Thermal decomposition of 4,5-benzotropone (11).
Scheme 27: Reaction of 4,5-benzotropone (11) with 1,2-ethanediol and 1,2-ethanedithiol.
Scheme 28: Conversions of 1-benzosuberone (162) to 2,3-benzotropone (12).
Scheme 29: Synthesis strategies for 2,3-bezotropone (12) using 1-benzosuberones.
Scheme 30: Oxidation-based synthesis of 2,3-benzotropone (12) via 1-benzosuberone (162).
Scheme 31: Synthesis of 2,3-benzotropone (12) from α-tetralone (171) via ring-expansion.
Scheme 32: Preparation of 2,3-benzotropone (12) by using of benzotropolone 174.
Figure 6: Benzoheptafulvenes as condensation products of 2,3-benzotropone (12).
Scheme 33: Conversion of 2,3-benzotropone (12) to tosylhydrazone salt 182 and gem-dichloride 187.
Figure 7: Benzohomoazocines 191–193 and benzoazocines 194–197.
Scheme 34: From 2,3-benzotropone (12) to carbonium ions 198–201.
Scheme 35: Cycloaddition reactions of 2,3-benzotropone (12).
Scheme 36: Reaction of 2,3-benzotropone (12) with various reagents and compounds.
Figure 8: 3,4-Benzotropone (13) and its resonance structure.
Scheme 37: Synthesis of 6,7-benzobicyclo[3.2.0]hepta-3,6-dien-2-one (230).
Figure 9: Photolysis and thermolysis products of 230.
Figure 10: Benzotropolones and their tautomeric structures.
Scheme 38: Synthesis strategies of 4,5-benzotropolone (238).
Scheme 39: Synthesis protocol for 2-hydroxy-4,5-benzotropone (238) using oxazole-benzo[7]annulene 247.
Figure 11: Some quinoxaline and pyrazine derivatives 254–256 prepared from 4,5-benzotropolone (238).
Scheme 40: Nitration product of 4,5-benzotropolone (238) and its isomerization to 1-nitro-naphthoic acid (259)....
Scheme 41: Synthesis protocol for 6-hydroxy-2,3-benzotropone (239) from benzosuberone (162).
Scheme 42: Various reactions via 6-hydroxy-2,3-benzotropone (239).
Scheme 43: Photoreaction of 6-hydroxy-2,3-benzotropone (239).
Scheme 44: Synthesis of 7-hydroxy-2,3-benzotropone (241) from benzosuberone (162).
Scheme 45: Synthesis strategy for 7-hydroxy-2,3-benzotropone (241) from ketone 276.
Scheme 46: Synthesis of 7-hydroxy-2,3-benzotropone (241) from β-naphthoquinone (280).
Scheme 47: Synthesis of 7-hydroxy-2,3-benzotropone (241) from bicyclic endoperoxide 213.
Scheme 48: Synthesis of 7-hydroxy-2,3-benzotropone (241) by ring-closing metathesis.
Figure 12: Various monosubstitution products 289–291 of 7-hydroxy-2,3-benzotropone (241).
Scheme 49: Reaction of 7-hydroxy-2,3-benzotropone (241) with various reagents.
Scheme 50: Synthesis of 4-hydroxy-2,3-benzotropones 174 and 304 from diketones 300/301.
Scheme 51: Catalytic hydrogenation of diketones 300 and 174.
Scheme 52: Synthesis of halo-benzotropones from alkoxy-naphthalenes 306, 307 and 310.
Figure 13: Unexpected byproducts 313–315 during synthesis of chlorobenzotropone 309.
Figure 14: Some halobenzotropones and their cycloadducts.
Scheme 53: Multisep synthesis of 2-chlorobenzotropone 309.
Scheme 54: A multistep synthesis of 2-bromo-benzotropone 26.
Scheme 55: A multistep synthesis of bromo-2,3-benzotropones 311 and 316.
Scheme 56: Oxidation reactions of 8-bromo-5H-benzo[7]annulene (329) with some oxidants.
Scheme 57: Synthesis of 2-bromo-4,5-benzotropone (26).
Scheme 58: Synthesis of 6-chloro-2,3-benzotropone (335) using LiCl and proposed intermediate 336.
Scheme 59: Reaction of 7-bromo-2,3-benzotropone (316) with methylamine.
Scheme 60: Reactions of bromo-2,3-benzotropones 26 and 311 with dimethylamine.
Scheme 61: Reactions of bromobenzotropones 311 and 26 with NaOMe.
Scheme 62: Reactions of bromobenzotropones 26 and 312 with t-BuOK in the presence of DPIBF.
Scheme 63: Cobalt-catalyzed reductive cross-couplings of 7-bromo-2,3-benzotropone (316) with cyclic α-bromo en...
Figure 15: Cycloadduct 357 and its di-π-methane rearrangement product 358.
Scheme 64: Catalytic hydrogenation of 2-chloro-4,5-benzotropone (311).
Scheme 65: Synthesis of dibromo-benzotropones from benzotropones.
Scheme 66: Bromination/dehydrobromination of benzosuberone (162).
Scheme 67: Some transformations of isomeric dibromo-benzotropones 261A/B.
Scheme 68: Transformations of benzotropolone 239B to halobenzotropolones 369–371.
Figure 16: Bromobenzotropolones 372–376 and 290 prepared via bromination/dehydrobromination strategy.
Scheme 69: Synthesis of some halobenzotropolones 289, 377 and 378.
Figure 17: Bromo-chloro-derivatives 379–381 prepared via chlorination.
Scheme 70: Synthesis of 7-iodo-3,4-benzotropolone (382).
Scheme 71: Hydrogenation of bromobenzotropolones 369 and 370.
Scheme 72: Debromination reactions of mono- and dibromides 290 and 375.
Figure 18: Nitratation and oxidation products of some halobenzotropolenes.
Scheme 73: Azo-coupling reactions of some halobenzotropolones 294, 375 and 378.
Figure 19: Four possible isomers of dibenzotropones 396–399.
Figure 20: Resonance structures of tribenzotropone (400).
Scheme 74: Two synthetic pathways for tribenzotropone (400).
Scheme 75: Synthesis of tribenzotropone (400) from dibenzotropone 399.
Scheme 76: Synthesis of tribenzotropone (400) from 9,10-phenanthraquinone (406).
Scheme 77: Synthesis of tribenzotropone (400) from trifluoromethyl-substituted arene 411.
Figure 21: Dibenzosuberone (414).
Figure 22: Reduction products 415 and 416 of tribenzotropone (400).
Figure 23: Structures of tribenzotropone dimethyl ketal 417 and 4-phenylfluorenone (412) and proposed intermed...
Figure 24: Structures of benzylidene- and methylene-9H-tribenzo[a,c,e][7]annulenes 419 and 420 and chiral phos...
Figure 25: Structures of tetracyclic alcohol 422, p-quinone methide 423 and cation 424.
Figure 26: Structures of host molecules 425–427.
Scheme 78: Synthesis of non-helical overcrowded derivatives syn/anti-431.
Figure 27: Hexabenzooctalene 432.
Figure 28: Structures of possible eight isomers 433–440 of naphthotropone.
Scheme 79: Synthesis of naphthotropone 437 starting from 1-phenylcycloheptene (441).
Scheme 80: Synthesis of 10-hydroxy-11H-cyclohepta[a]naphthalen-11-one (448) from diester 445.
Scheme 81: Synthesis of naphthotropone 433.
Scheme 82: Synthesis of naphthotropones 433 and 434 via cycloaddition reaction.
Scheme 83: Synthesis of naphthotropone 434 starting from 452.
Figure 29: Structures of tricarbonyl(tropone)irons 458, and possible cycloadducts 459.
Scheme 84: Synthesis of naphthotropone 436.
Scheme 85: Synthesis of precursor 465 for naphthotropone 435.
Scheme 86: Generation of naphthotropone 435 from 465.
Figure 30: Structures of tropylium cations 469 and 470.
Figure 31: Structures of tropylium ions 471+.BF4−, 472+.BF4−, and 473+.BF4−.
Scheme 87: Synthesis of tropylium ions 471+.BF4− and 479+.ClO4−.
Scheme 88: Synthesis of 1- and 2-methylanthracene (481 and 482) via carbene–carbene rearrangement.
Figure 32: Trapping products 488–490.
Scheme 89: Generation and chemistry of a naphthoannelated cycloheptatrienylidene-cycloheptatetraene intermedia...
Scheme 90: Proposed intermediates and reaction pathways for adduct 498.
Scheme 91: Exited-state intramolecular proton transfer of 505.
Figure 33: Benzoditropones 506 and 507.
Scheme 92: Synthesis of benzoditropone 506e.
Scheme 93: Synthetic approaches for dibenzotropone 507 via tropone (1).
Scheme 94: Formation mechanisms of benzoditropone 507 and 516 via 515.
Scheme 95: Synthesis of benzoditropones 525 and 526 from pyromellitic dianhydride (527).
Figure 34: Possible three benzocyclobutatropones 534–536.
Scheme 96: Synthesis of benzocyclobutatropones 534 and 539.
Scheme 97: Synthesis attempts for benzocyclobutatropone 545.
Scheme 98: Generation and trapping of symmetric benzocyclobutatropone 536.
Scheme 99: Synthesis of chloro-benzocyclobutatropone 552 and proposed mechanism of fluorenone derivatives.
Scheme 100: Synthesis of tropolone analogue 559.
Scheme 101: Synthesis of tropolones 561 and 562.
Figure 35: o/p-Tropoquinone rings (563 and 564) and benzotropoquinones (565–567).
Scheme 102: Synthesis of benzotropoquinone 566.
Scheme 103: Synthesis of benzotropoquinone 567 via a Diels–Alder reaction.
Figure 36: Products 575–577 through 1,2,3-benzotropoquinone hydrate 569.
Scheme 104: Structures 578–582 prepared from tropoquinone 567.
Figure 37: Two possible structures 583 and 584 for dibenzotropoquinone, and precursor compound 585 for 583.
Scheme 105: Synthesis of saddle-shaped ketone 592 using dibenzotropoquinone 584.
A new and efficient procedure for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones
- Marcelo Isidoro P. Reis,
- Vinícius R. Campos,
- Jackson A. L. C. Resende,
- Fernando C. Silva and
- Vitor F. Ferreira
Beilstein J. Org. Chem. 2015, 11, 1235–1240, doi:10.3762/bjoc.11.137
- , Campus do Valonguinho, 24020-150, Niterói, RJ, Brazil 10.3762/bjoc.11.137 Abstract A new and efficient method for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones in one step with high yields from the reaction of lawsone with 1,3,5-triazinanes was developed. Keywords: hydrobenzo[g
- pyrrole-, furan- and thiophene-fused naphthoquinones [36]. For several years, our group has been interested in developing new synthetic methods for the preparation of heterocycle-fused 1,4-naphthoquinones or heterocycle-tethered 1,4-naphthoquinones. 1,3-Quinazolines are nitrogenated heterocycles that are
- present in several products. However, there are only three procedures for the preparation of hexahydropyrimidine-fused 1,4-naphthoquinones available. Some of them are restrictive, troublesome and produce the hexahydropyrimidine-1,4-naphthoquinones in low yields. Möhrle and Herbruggen synthesized
Graphical Abstract
Figure 1: General template for heterocycle-fused 1,4-naphthoquinones.
Scheme 1: Methods for the preparation of hexahydropyrimidine-fused 1,4-naphthoquinones.
Scheme 2: Synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones 13 and 21–25.
Figure 2: ORTEP diagram of compound 18 depicted with ellipsoids drawn at the 50% probability level and the at...
Figure 3: ORTEP diagram of compound 23 depicted with ellipsoids drawn at the 50% probability level and the at...
Scheme 3: Proposed mechanism for the formation of 13 and 21–25.
Cross-dehydrogenative coupling for the intermolecular C–O bond formation
- Igor B. Krylov,
- Vera A. Vil’ and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13
Graphical Abstract
Scheme 1: Cross-dehydrogenative coupling.
Scheme 2: Cross-dehydrogenative C–O coupling.
Scheme 3: Regioselective ortho-acetoxylation of meta-substituted arylpyridines and N-arylamides.
Scheme 4: ortho-Acyloxylation and alkoxylation of arenes directed by pyrimidine, benzoxazole, benzimidazole a...
Scheme 5: Cu(OAc)2/AgOTf/O2 oxidative system in the ortho-alkoxylation of arenes.
Scheme 6: Pd(OAc)2/persulfate oxidative system in the ortho-alkoxylation and acetoxylation of arenes with nit...
Scheme 7: ortho-Acetoxylation and methoxylation of O-methyl aryl oximes, N-phenylpyrrolidin-2-one, and (3-ben...
Scheme 8: Ruthenium-catalyzed ortho-acyloxylation of acetanilides.
Scheme 9: Acetoxylation and alkoxylation of arenes with amide directing group using Pd(OAc)2/PhI(OAc)2 oxidat...
Scheme 10: Alkoxylation of azoarenes, 2-aryloxypyridines, picolinamides, and N-(1-methyl-1-(pyridin-2-yl)ethyl...
Scheme 11: Acetoxylation of compounds containing picolinamide and quinoline-8-amine moieties using the Pd(OAc)2...
Scheme 12: (CuOH)2CO3 catalyzed oxidative ortho-etherification using air as oxidant.
Scheme 13: Copper-catalyzed aerobic alkoxylation and aryloxylation of arenes containing pyridine-N-oxide moiet...
Scheme 14: Cobalt-catalyzed aerobic alkoxylation of arenes and alkenes containing pyridine N-oxide moiety.
Scheme 15: Non-symmetric double-fold C–H ortho-acyloxylation.
Scheme 16: N-nitroso directed ortho-alkoxylation of arenes.
Scheme 17: Selective alkoxylation and acetoxylation of alkyl groups.
Scheme 18: Acetoxylation of 2-alkylpyridines and related compounds.
Scheme 19: Acyloxylation and alkoxylation of alkyl fragments of substrates containing amide or sulfoximine dir...
Scheme 20: Palladium-catalyzed double sp3 C–H alkoxylation of N-(quinolin-8-yl)amides for the synthesis of sym...
Scheme 21: Copper-catalyzed acyloxylation of methyl groups of N-(quinolin-8-yl)amides.
Scheme 22: One-pot acylation and sp3 C–H acetoxylation of oximes.
Scheme 23: Possible mechanism of oxidative esterification catalyzed by N-heterocyclic nucleophilic carbene.
Scheme 24: Oxidative esterification employing stoichiometric amounts of aldehydes and alcohols.
Scheme 25: Selective oxidative coupling of aldehydes with alcohols in the presence of amines.
Scheme 26: Iodine mediated oxidative esterification.
Scheme 27: Oxidative C–O coupling of benzyl alcohols with methylarenes under the action of Bu4NI/t-BuOOH syste...
Scheme 28: Oxidative coupling of methyl- and ethylarenes with aromatic aldehydes under the action of Bu4NI/t-B...
Scheme 29: Cross-dehydrogenative C–O coupling of aldehydes with t-BuOOH in the presence of Bu4NI.
Scheme 30: Bu4NI-catalyzed α-acyloxylation reaction of ethers and ketones with aldehydes and t-BuOOH.
Scheme 31: Oxidative coupling of aldehydes with N-hydroxyimides and hexafluoroisopropanol.
Scheme 32: Oxidative coupling of alcohols with N-hydroxyimides.
Scheme 33: Oxidative coupling of aldehydes and primary alcohols with N-hydroxyimides using (diacetoxyiodo)benz...
Scheme 34: Proposed mechanism of the oxidative coupling of aldehydes and N-hydroxysuccinimide under action of ...
Scheme 35: Oxidative coupling of aldehydes with pivalic acid (172).
Scheme 36: Oxidative C–O coupling of aldehydes with alkylarenes using the Cu(OAc)2/t-BuOOH system.
Scheme 37: Copper-catalyzed acyloxylation of C(sp3)-H bond adjacent to oxygen in ethers using benzyl alcohols.
Scheme 38: Oxidative C–O coupling of aromatic aldehydes with cycloalkanes.
Scheme 39: Ruthenium catalyzed cross-dehydrogenative coupling of primary and secondary alcohols.
Scheme 40: Cross-dehydrogenative C–O coupling reactions of β-dicarbonyl compounds with sulfonic acids, acetic ...
Scheme 41: Acyloxylation of ketones, aldehydes and β-dicarbonyl compounds using carboxylic acids and Bu4NI/t-B...
Scheme 42: Acyloxylation of ketones using Bu4NI/t-BuOOH system.
Scheme 43: Cross-dehydrogenative C–O coupling of β-dicarbonyl compounds and their heteroanalogues with N-hydro...
Scheme 44: Cross-dehydrogenative C–O coupling of β-dicarbonyl compounds and their heteroanalogues with t-BuOOH....
Scheme 45: Oxidative C–O coupling of 2,6-dialkylphenyl-β-keto esters and thioesters with tert-butyl hydroxycar...
Scheme 46: α’-Acyloxylation of α,β-unsaturated ketones using KMnO4.
Scheme 47: Possible mechanisms of the acetoxylation at the allylic position of alkenes by Pd(OAc)2.
Scheme 48: Products of the oxidation of terminal alkenes by Pd(II)/AcOH/oxidant system.
Scheme 49: Acyloxylation of terminal alkenes with carboxylic acids.
Scheme 50: Synthesis of linear E-allyl esters by cross-dehydrogenative coupling of terminal alkenes wih carbox...
Scheme 51: Pd(OAc)2-catalyzed acetoxylation of Z-vinyl(triethylsilanes).
Scheme 52: α’-Acetoxylation of α-acetoxyalkenes with copper(II) chloride in acetic acid.
Scheme 53: Oxidative acyloxylation at the allylic position of alkenes and at the benzylic position of alkylare...
Scheme 54: Copper-catalyzed alkoxylation of methylheterocyclic compounds using di-tert-butylperoxide as oxidan...
Scheme 55: Oxidative C–O coupling of methylarenes with β-dicarbonyl compounds or phenols.
Scheme 56: Copper-catalyzed esterification of methylbenzenes with cyclic ethers and cycloalkanes.
Scheme 57: Oxidative C–O coupling of carboxylic acids with toluene catalyzed by Pd(OAc)2.
Scheme 58: Oxidative acyloxylation at the allylic position of alkenes with carboxylic acids using the Bu4NI/t-...
Scheme 59: Cross-dehydrogenative C–O coupling of carboxylic acids with alkylarenes using the Bu4NI/t-BuOOH sys...
Scheme 60: Oxidative C–O cross-coupling of methylarenes with ethyl or isopropylarenes.
Scheme 61: Phosphorylation of benzyl C–H bonds using the Bu4NI/t-BuOOH oxidative system.
Scheme 62: Selective C–H acetoxylation of 2,3-disubstituted indoles.
Scheme 63: Acetoxylation of benzylic position of alkylarenes using DDQ as oxidant.
Scheme 64: C–H acyloxylation of diarylmethanes, 3-phenyl-2-propen-1-yl acetate and dimethoxyarene using DDQ.
Scheme 65: Cross-dehydrogenative C–O coupling of 1,3-diarylpropylenes and 1,3-diarylpropynes with alcohols.
Scheme 66: One-pot azidation and C–H acyloxylation of 3-chloro-1-arylpropynes.
Scheme 67: Cross-dehydrogenative C–O coupling of 1,3-diarylpropylenes, (E)-1-phenyl-2-isopropylethylene and is...
Scheme 68: Cross-dehydrogenative C–O coupling of alkylarenes and related compounds with N-hydroxyphthalimide.
Scheme 69: Acetoxylation at the benzylic position of alkylarenes mediated by N-hydroxyphthalimide.
Scheme 70: C–O coupling of methylarenes with aromatic carboxylic acids employing the NaBrO3/NaHSO3 system.
Scheme 71: tert-Butyl peroxidation of allyl, propargyl and benzyl ethers catalyzed by Fe(acac)3.
Scheme 72: Cross-dehydrogenative C–O coupling of ethers with carboxylic acids mediated by Bu4NI/t-BuOOH system....
Scheme 73: Oxidative acyloxylation of dimethylamides and dioxane with 2-aryl-2-oxoacetic acids accompanied by ...
Scheme 74: tert-Butyl peroxidation of N-benzylamides and N-allylbenzamide using the Bu4NI/t-BuOOH system.
Scheme 75: Cross-dehydrogenative C–O coupling of aromatic carboxylic acids with ethers using Fe(acac)3 as cata...
Scheme 76: Cross-dehydrogenative C–O coupling of cyclic ethers with 2-hydroxybenzaldehydes using iron carbonyl...
Scheme 77: Cross-dehydrogenative C–O coupling of ethers with β-dicarbonyl compounds and phenols using copper c...
Scheme 78: Cross-dehydrogenative C–O coupling of 2-hydroxybenzaldehyde with dioxane catalyzed by Cu2(BPDC)2(BP...
Scheme 79: Ruthenium chloride-catalyzed acyloxylation of β-lactams.
Scheme 80: Ruthenium-catalyzed tert-butyl peroxydation amides and acetoxylation of β-lactams.
Scheme 81: PhI(OAc)2-mediated α,β-diacetoxylation of tertiary amines.
Scheme 82: Electrochemical oxidative methoxylation of tertiary amines.
Scheme 83: Cross-dehydrogenative C–O coupling of ketene dithioacetals with carboxylic acids in the presence of...
Scheme 84: Cross-dehydrogenative C–O coupling of enamides with carboxylic acids using iodosobenzene as oxidant....
Scheme 85: Oxidative alkoxylation, acetoxylation, and tosyloxylation of acylanilides using PhI(O(O)CCF3)2 in t...
Scheme 86: Proposed mechanism of the oxidative C–O coupling of actetanilide with O-nucleophiles in the presenc...
Scheme 87: Three-component coupling of aldehydes, anilines and alcohols involving oxidative intermolecular C–O...
Scheme 88: Oxidative coupling of phenols with alcohols.
Scheme 89: 2-Acyloxylation of quinoline N-oxides with arylaldehydes in the presence of the CuOTf/t-BuOOH syste...
Scheme 90: Cross-dehydrogenative C–O coupling of azoles with primary alcohols.
Scheme 91: Oxidation of dipyrroles to dipyrrins and subsequent oxidative alkoxylation in the presence of Na3Co...
Scheme 92: Oxidative dehydrogenative carboxylation of alkanes and cycloalkanes to allylic esters.
Scheme 93: Pd-catalyzed acetoxylation of benzene.
Oxidative phenylamination of 5-substituted 1-hydroxynaphthalenes to N-phenyl-1,4-naphthoquinone monoimines by air and light “on water”
- Julio Benites,
- Juan Meléndez,
- Cynthia Estela,
- David Ríos,
- Luis Espinoza,
- Iván Brito and
- Jaime A. Valderrama
Beilstein J. Org. Chem. 2014, 10, 2448–2452, doi:10.3762/bjoc.10.255
- [1][2][3][4][5][6]. In this context, the sunlight-induced synthesis of 5-hydroxy-1,4-naphthoquinone (2, juglone, Figure 1) by sensitized phothooxygenation of 1,5-dihydroxynaphthalene (1, 1,5-DHN) [7] and the preparation of 2-phenylamino-1,4-naphthoquinones by reaction of 1,4-naphthoquinones with
- phenylamines “on water” [8] represent two valuable examples on the scope of green methodologies in the field of quinone synthesis. 1,4-Naphthoquinones possessing a substituted amino group in the 2-position have been the subject of study for many years due to their use in a variety of medical and biological
Graphical Abstract
Figure 1: Structures of compounds 1–3.
Scheme 1: Hypothetical one-pot synthesis of compound 4a and/or 4b.
Figure 2: Structure of compound 6 determined by single crystal X-ray diffractometry.
Scheme 2: Evaluation of the substrate scope using RB as oxygen (1O2) sensitizer “on water”.
Scheme 3: Evaluation of the oxidative coupling in the absence of RB, on water.
Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones and novel ring contraction and fusion reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] into 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones
- Lidia S. Konstantinova,
- Kirill A. Lysov,
- Ljudmila I. Souvorova and
- Oleg A. Rakitin
Beilstein J. Org. Chem. 2013, 9, 577–584, doi:10.3762/bjoc.9.62
- one of the most interesting modifications. In fact, 2-alkylthio-1,4-naphthoquinones were found to show cell-growth inhibitory properties [2], and dihydrothienonaphthoquinones appeared to be potent antitumour compounds [3]. In searching for agents with better pharmacological properties, wider activity
- range, and low side effects it seemed quite promising to incorporate two heteroatoms into the heterocycle attached to the naphthoquinone (e.g., thiazole) core. Despite continuous interest in 1,4-naphthoquinones fused with heterocycles, only a limited number of thiazolonaphthoquinones have been known so
Graphical Abstract
Scheme 1: Retrosynthetic analysis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[...
Scheme 2: Reaction of 2-[butyl(methyl)amino]naphthoquinone 3a with S2Cl2 and Hünig’s base.
Scheme 3: Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones 1.
Scheme 4: Synthesis of 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones 2.
Scheme 5: Reaction of N-substituted 2-(methylamino)anthracene-1,4-diones 4 with S2Cl2 and Hünig’s base.
Scheme 6: Synthesis of thiazole-2-thiones 10c and 11 from quinonothiazoles 1c and 2c.
Scheme 7: A plausible mechanism for the formation of naphtho- and anthraquinonothiazoles.
Scheme 8: Synthesis of 5-methyl-2,3,4,5-tetrahydro-1H-benzo[b]carbazole-6,11-dione (15) and 5-methyl-2,3,4,5-...
Scheme 9: A plausible mechanism for the conversion of spiro compounds 1d or 2d into carbazolediones 15 and 16....
Enantioselective Michael addition of 2-hydroxy-1,4-naphthoquinones to nitroalkenes catalyzed by binaphthyl-derived organocatalysts
- Saet Byeol Woo and
- Dae Young Kim
Beilstein J. Org. Chem. 2012, 8, 699–704, doi:10.3762/bjoc.8.78
- Saet Byeol Woo Dae Young Kim Department of Chemistry, Soonchunhyang University, Asan, Chungnam, 336-745, Korea 10.3762/bjoc.8.78 Abstract The highly enantioselective Michael addition of 2-hydroxy-1,4-naphthoquinones to nitroalkenes, promoted by binaphthyl-modified chiral bifunctional
- organocatalysts is described. This reaction afforded the chiral functionalized naphthoquinones in high yields (81–95%) and excellent enantioselectivities (91–98% ee) under low catalyst loading (1 mol %). Keywords: asymmetric catalysis; Michael addition; 1,4-naphthoquinones; nitroalkenes; organocatalysis
- to the development of asymmetric conjugate additions of 1,3-dicarbonyl compounds to various Michael acceptors [27][28][29][30][31][32][33]. Recently, the groups of Du and Zhou reported a highly enantioselective Michael addition of 2-hydroxy-1,4-naphthoquinones to nitroalkenes catalyzed by chiral
Variations in product in reactions of naphthoquinone with primary amines
- Marjit W. Singh,
- Anirban Karmakar,
- Nilotpal Barooah and
- Jubaraj B. Baruah
Beilstein J. Org. Chem. 2007, 3, No. 10, doi:10.1186/1860-5397-3-10
- 2 are characterized by X-ray crystallography; they have hydrogen-bonded dimeric structures. Similar reaction of 1,4-naphthoquinone with 3-picolylamine and 4-picolylamine gives the corresponding 2-amino 1,4-naphthoquinones; two products are characterized by X-ray crystallography. The reaction of 1,4
- -benzoquinone reacts with primary amines to give 2,5-diamino 1,4-benzoquinones; similar reaction of 1,4-naphthoquinone with primary amines results in the formation of 2-amino 1,4-naphthoquinones. [13] However, the product formed from such simple reaction of amine with various quinones has much scope for
- in the pyridine ring. [23] Thus, we prepared two picolyl derivatives of 1,4-naphthoquinone from independent reactions of 3-picolylamine and 4-picolylamine with 1,4-naphthoquinone. These reactions resulted in the corresponding 2-amino substituted 1,4-naphthoquinones as illustrated in Scheme 3. The
Graphical Abstract
Scheme 1: Reaction of 1,2-naphthoquinone with primary amines.
Figure 1: The solid state structure of (a) 1 and (b) 2 (drawn with 20% thermal ellipsoids).
Scheme 2: Equivalence of reactivity between 1,2 and 1,4-naphthoquinone.
Scheme 3: The reaction of picolylamine with 1,4-naphthoquinone.
Figure 2: (a) The crystal structure of 3 and (b) weak interactions in 3 leading to self-assembly, (c) Structu...
Scheme 4: The reaction of 1,4-naphthoquinone with 4-aminothiophenol and 4-aminophenol.
Figure 3: The 1HNMR spectra (400 MHz) of the reaction mixture of 1,4-naphthoquinone with 4-amino thiophenol (...
Figure 4: The structure of the products from the reaction of 1,4-naphthoquinone with (a) 4-aminothiophenol (b...
