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Search for "trifluoroacetic acid" in Full Text gives 315 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Interactions between shape-persistent macromolecules as probed by AFM
- Johanna Blass,
- Jessica Brunke,
- Franziska Emmerich,
- Cédric Przybylski,
- Vasil M. Garamus,
- Artem Feoktystov,
- Roland Bennewitz,
- Gerhard Wenz and
- Marcel Albrecht
Beilstein J. Org. Chem. 2017, 13, 938–951, doi:10.3762/bjoc.13.95
- 4 was prepared by Sonogashira reaction of 3 with trimethylsilylacetylene. Subsequent deprotection of the TMS groups using tetra-n-butylammonium fluoride and saponification of the tert-butyl ester with trifluoroacetic acid resulted in the corresponding benzoic acid 6. The latter was coupled to 6
Graphical Abstract
Figure 1: Interaction of a shape-persistent CD polymer with ditopic guests.
Figure 2: Schematic representation of tip and surface modifications realized in this study (bottom). Blue lin...
Scheme 1: Synthesis of the CD polymer. a) conc. HNO3, reflux, 6 d; b) tert-butanol, cat. H2SO4, MgSO4, CH2Cl2...
Figure 3: Absorption spectra of monomer 7 (solid red line) and polymer 8 (solid blue line) in water. Emission...
Figure 4: Positive linear MALDI–TOF spectrum of polymer 8 using HABA/TMG2 matrix.
Figure 5: SANS data for polymer 8 and fit by cylindrical model (solid line).
Scheme 2: Ditopic and monotopic guest molecules.
Figure 6: Solubility of polymer 8 in the presence of ditopic connector 9 (black graph) and 1-aminoadamantane ...
Scheme 3: Synthesis of amino functionalized polymer 12.
Figure 7: Characteristic force curves recorded during retraction of the AFM tip from the surface. Four functi...
Figure 8: Graphical summary of experimental results for the four configurations of CD attachment introduced i...
Figure 9: (a) Detail of the end of a force curve for a polymer-functionalized tip retracted from a polymer-fu...
Figure 10: Characteristic result of a friction experiment for a polymer-functionalized tip sliding on a surfac...
Synthesis of new pyrrolidine-based organocatalysts and study of their use in the asymmetric Michael addition of aldehydes to nitroolefins
- Alejandro Castán,
- Ramón Badorrey,
- José A. Gálvez and
- María D. Díaz-de-Villegas
Beilstein J. Org. Chem. 2017, 13, 612–619, doi:10.3762/bjoc.13.59
- of the benzylic group with molecular hydrogen using Pd(OH)2/C as a catalyst in the presence of trifluoroacetic acid, b) reprotection of the amino group as benzylcarbamate by treatment of the crude reaction mixture with benzyl chloroformate in the presence of diisopropylethylamine, c) hydrolysis of
- the dioxolane moiety with trifluoroacetic acid, d) reconstruction of the dioxolane moiety by reaction of the diol with the corresponding dimethoxyacetal in the presence of SnCl2 and e) N-deprotection of the pyrrolidine by exposure of the benzylcarbamate to molecular hydrogen in the presence of
- for the diastereoselectivity and syn-enantioselectivity. On the other hand, in the presence of trifluoroacetic acid the reaction proceeded slowly and the diastereoselectivity decreased to some extent. The presence of an achiral thiourea did not improve the results. Finally, we considered the
Graphical Abstract
Figure 1: Strategy for the preparation of 2-substituted pyrrolidines C.
Scheme 1: Synthesis of the new organocatalyst OC1.
Scheme 2: Synthesis of new organocatalyst OC2.
Scheme 3: Synthesis of new organocatalyst OC3.
Scheme 4: Synthesis of new organocatalysts OC4–OC10.
Scheme 5: Synthesis of new organocatalyst OC11.
Synthesis of 1-indanones with a broad range of biological activity
- Marika Turek,
- Dorota Szczęsna,
- Marek Koprowski and
- Piotr Bałczewski
Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48
- in the range of 10–880 nM [66]. The synthesized compounds have also shown a strong inhibition of tubulin polymerase with IC50 values in the range of 0.62–2.04 µM. In this synthesis, the chalcone 124 underwent a Nazarov cyclization in the presence of trifluoroacetic acid to give 1-indanone 125. 2
- interesting bromo reagent for further transformations, has been synthesized from chalcone 128 [67]. In this synthesis, a Nazarov reaction of chalcone 128, in the presence of trifluoroacetic acid, gave 6-methoxy-3-phenyl-1-indanone 129 in 88% yield followed by the reaction with bromine in diethyl ether to give
- the presence of trifluoroacetic acid (TFA) at 120 °C (4 hours). The authors have proved that the microwave heating would significantly shorten the reaction time up to 20 minutes under the same reaction conditions (TFA, 120 °C, Scheme 42). The cell growth inhibitory properties of the synthesized 1
Graphical Abstract
Figure 1: Biologically active 1-indanones and their structural analogues.
Figure 2: Number of papers about (a) 1-indanones, (b) synthesis of 1-indanones.
Scheme 1: Synthesis of 1-indanone (2) from hydrocinnamic acid (1).
Scheme 2: Synthesis of 1-indanone (2) from 3-(2-bromophenyl)propionic acid (3).
Scheme 3: Synthesis of 1-indanones 5 from 3-arylpropionic acids 4.
Scheme 4: Synthesis of kinamycin (9a) and methylkinamycin C (9b).
Scheme 5: Synthesis of trifluoromethyl-substituted arylpropionic acids 12, 1-indanones 13 and dihydrocoumarin...
Scheme 6: Synthesis of 1-indanones 16 from benzoic acids 15.
Scheme 7: Synthesis of 1-indanones 18 from arylpropionic and 3-arylacrylic acids 17.
Scheme 8: The NbCl5-induced one-step synthesis of 1-indanones 22.
Scheme 9: Synthesis of biologically active 1-indanone derivatives 26.
Scheme 10: Synthesis of enantiomerically pure indatraline ((−)-29).
Scheme 11: Synthesis of 1-indanone (2) from the acyl chloride 30.
Scheme 12: Synthesis of the mechanism-based inhibitors 33 of coelenterazine.
Scheme 13: Synthesis of the indane 2-imidazole derivative 37.
Scheme 14: Synthesis of fluorinated PAHs 41.
Scheme 15: Synthesis of 1-indanones 43 via transition metal complexes-catalyzed carbonylative cyclization of m...
Scheme 16: Synthesis of 6-methyl-1-indanone (46).
Scheme 17: Synthesis of 1-indanone (2) from ester 48.
Scheme 18: Synthesis of benzopyronaphthoquinone 51 from the spiro-1-indanone 50.
Scheme 19: Synthesis of the selective endothelin A receptor antagonist 55.
Scheme 20: Synthesis of 1-indanones 60 from methyl vinyl ketone (57).
Scheme 21: Synthesis of 1-indanones 64 from diethyl phthalate 61.
Scheme 22: Synthesis of 1-indanone derivatives 66 from various Meldrum’s acids 65.
Scheme 23: Synthesis of halo 1-indanones 69.
Scheme 24: Synthesis of substituted 1-indanones 71.
Scheme 25: Synthesis of spiro- and fused 1-indanones 73 and 74.
Scheme 26: Synthesis of spiro-1,3-indanodiones 77.
Scheme 27: Mechanistic pathway for the NHC-catalyzed Stetter–Aldol–Michael reaction.
Scheme 28: Synthesis of 2-benzylidene-1-indanone derivatives 88a–d.
Scheme 29: Synthesis of 1-indanone derivatives 90a–i.
Scheme 30: Synthesis of 1-indanones 96 from o-bromobenzaldehydes 93 and alkynes 94.
Scheme 31: Synthesis of 3-hydroxy-1-indanones 99.
Scheme 32: Photochemical preparation of 1-indanones 103 from ketones 100.
Scheme 33: Synthesis of chiral 3-aryl-1-indanones 107.
Scheme 34: Photochemical isomerization of 2-methylbenzil 108.
Scheme 35: Synthesis of 2-hydroxy-1-indanones 111a–c.
Scheme 36: Synthesis of 1-indanone derivatives 113 and 114 from η6-1,2-dioxobenzocyclobutene complex 112.
Scheme 37: Synthesis of nakiterpiosin (117).
Scheme 38: Synthesis of 2-alkyl-1-indanones 120.
Scheme 39: Synthesis of fluorine-containing 1-indanone derivatives 123.
Scheme 40: Synthesis of 2-benzylidene and 2-benzyl-1-indanones 126, 127 from the chalcone 124.
Scheme 41: Synthesis of 2-bromo-6-methoxy-3-phenyl-1-indanone (130).
Scheme 42: Synthesis of combretastatin A-4-like indanones 132a–s.
Figure 3: Chemical structures of investigated dienones 133 and synthesized cyclic products 134–137.
Figure 4: Chemical structures of 1-indanones and their heteroatom analogues 138–142.
Scheme 43: Synthesis of 2-phosphorylated and 2-non-phosphorylated 1-indanones 147 and 148 from β-ketophosphona...
Scheme 44: Photochemical synthesis of 1-indanone derivatives 150, 153a, 153b.
Scheme 45: Synthesis of polysubstituted-1-indanones 155, 157.
Scheme 46: Synthesis of 1-indanones 159a–g from α-arylpropargyl alcohols 158 using RhCl(PPh3)3 as a catalyst.
Scheme 47: Synthesis of optically active 1-indanones 162 via the asymmetric Rh-catalyzed isomerization of race...
Scheme 48: Mechanism of the Rh-catalyzed isomerization of α-arylpropargyl alcohols 161 to 1-indanones 162.
Figure 5: Chemical structure of abicoviromycin (168) and its new benzo derivative 169.
Scheme 49: Synthesis of racemic benzoabicoviromycin 172.
Scheme 50: Synthesis of [14C]indene 176.
Scheme 51: Synthesis of indanone derivatives 178–180.
Scheme 52: Synthesis of racemic pterosin A 186.
Scheme 53: Synthesis of trans-2,3-disubstituted 1-indanones 189.
Scheme 54: Synthesis of 3-aryl-1-indanone derivatives 192.
Scheme 55: Synthesis of 1-indanone derivatives 194 from 3-(2-iodoaryl)propanonitriles 193.
Scheme 56: Synthesis of 1-indanones 200–204 by cyclization of aromatic nitriles.
Scheme 57: Synthesis of 1,1’-spirobi[indan-3,3’-dione] derivative 208.
Scheme 58: Total synthesis of atipamezole analogues 211.
Scheme 59: Synthesis of 3-[4-(1-piperidinoethoxy)phenyl]spiro[indene-1,1’-indan]-5,5’-diol hydrochloride 216.
Scheme 60: Synthesis of 3-arylindan-1-ones 219.
Scheme 61: Synthesis of 2-hydroxy-1-indanones 222.
Scheme 62: Synthesis of the 1-indanone 224 from the THP/MOM protected chalcone epoxide 223.
Scheme 63: Synthesis of 1-indanones 227 from γ,δ-epoxy ketones 226.
Scheme 64: Synthesis of 2-hydroxy-2-methylindanone (230).
Scheme 65: Synthesis of 1-indanone derivatives 234 from cyclopropanol derivatives 233.
Scheme 66: Synthesis of substituted 1-indanone derivatives 237.
Scheme 67: Synthesis of 7-methyl substituted 1-indanone 241 from 1,3-pentadiene (238) and 2-cyclopentenone (239...
Scheme 68: Synthesis of disubstituted 1-indanone 246 from the siloxydiene 244 and 2-cyclopentenone 239.
Scheme 69: Synthesis of 5-hydroxy-1-indanone (250) via the Diels–Alder reaction of 1,3-diene 248 with sulfoxid...
Scheme 70: Synthesis of halogenated 1-indanones 253a and 253b.
Scheme 71: Synthesis of 1-indanones 257 and 258 from 2-bromocyclopentenones 254.
Scheme 72: Synthesis of 1-indanone 261 from 2-bromo-4-acetoxy-2-cyclopenten-1-one (260) and 1,2-dihydro-4-viny...
Scheme 73: Synthesis of 1-indanone 265 from 1,2-dihydro-7-methoxy-4-vinylnaphthalene (262) and bromo-substitut...
Scheme 74: Synthesis of 1-indanone 268 from dihydro-3-vinylphenanthrene 266 and 4-acetoxy-2-cyclopenten-1-one (...
Scheme 75: Synthesis of 1-indanone 271 from phenylselenyl-substituted cyclopentenone 268.
Scheme 76: Synthesis of 1-indanone 272 from the trienone 270.
Scheme 77: Synthesis of the 1-indanone 276 from the aldehyde 273.
Scheme 78: Synthesis of 1-indanones 278 and 279.
Scheme 79: Synthesis of 1-indanone 285 from octa-1,7-diyne (282) and cyclopentenone 239.
Scheme 80: Synthesis of benz[f]indan-1-one (287) from cyclopentenone 239 and o-bis(dibromomethyl)benzene (286)....
Scheme 81: Synthesis of 3-methyl-substituted benz[f]indan-1-one 291 from o-bis(dibromomethyl)benzene (286) and...
Scheme 82: Synthesis of benz[f]indan-1-one (295) from the anthracene epidioxide 292.
Scheme 83: Synthesis of 1-indanone 299 from homophthalic anhydride 298 and cyclopentynone 297.
Scheme 84: Synthesis of cyano-substituted 1-indanone derivative 301 from 2-cyanomethylbenzaldehyde (300) and c...
Scheme 85: Synthesis of 1-indanone derivatives 303–305 from ketene dithioacetals 302.
Scheme 86: Synthesis of 1-indanones 309–316.
Scheme 87: Mechanism of the hexadehydro-Diels–Alder (HDDA) reaction.
Scheme 88: Synthesis of 1-indenone 318 and 1-indanones 320 and 321 from tetraynes 317 and 319.
Scheme 89: Synthesis of 1-indanone 320 from the triyn 319.
Scheme 90: Synthesis 1-indanone 328 from 2-methylfuran 324.
Scheme 91: Synthesis of 1-indanones 330 and 331 from furans 329.
Scheme 92: Synthesis of 1-indanone 333 from the cycloadduct 332.
Scheme 93: Synthesis of (S)-3-arylindan-1-ones 335.
Scheme 94: Synthesis of (R)-2-acetoxy-1-indanone 338.
Figure 6: Chemical structures of obtained cyclopenta[α]phenanthrenes 339.
Scheme 95: Synthesis of the benzoindanone 343 from arylacetaldehyde 340 with 1-trimethylsilyloxycyclopentene (...
Biomimetic synthesis and HPLC–ECD analysis of the isomers of dracocephins A and B
- Viktor Ilkei,
- András Spaits,
- Anita Prechl,
- Áron Szigetvári,
- Zoltán Béni,
- Miklós Dékány,
- Csaba Szántay Jr,
- Judit Müller,
- Árpád Könczöl,
- Ádám Szappanos,
- Attila Mándi,
- Sándor Antus,
- Ana Martins,
- Attila Hunyadi,
- György Tibor Balogh,
- György Kalaus (†),
- Hedvig Bölcskei,
- László Hazai and
- Tibor Kurtán
Beilstein J. Org. Chem. 2016, 12, 2523–2534, doi:10.3762/bjoc.12.247
- assignment. The separation of the stereoisomers of dracocephins B 3a–d could be performed on an analytical Chiralpak IC column using the eluent acetonitrile/2-propanol/trifluoroacetic acid 90:10:0.1 (Figure 9a). Only partial separation could be achieved for the first two eluting stereosiomers, which was
Graphical Abstract
Figure 1: Structures of (±)-naringenin, (±)-dracocephins A1–A4 and B1–B4 with the indication of the absolute ...
Scheme 1: Proposed biosynthetic route to dracocephins A and B.
Scheme 2: Synthesis of (±)-5-ethoxypyrrolidine-2-one ((±)-9).
Scheme 3: Synthesis of (±)-dracocephins A and B (±)-2a–d and (±)-3a–d and the elution order of stereoisomers ...
Figure 2: a) Chiral HPLC–UV and HPLC–ECD traces of dracocephins A (2a–d) using Chiralpak IC column with the e...
Figure 3: Structure and population of the low-energy CAM-B3LYP/TZVP PCM/CHCl3 conformers (>2%) of (R)-1.
Figure 4: Experimental HPLC–ECD spectrum of (R)-naringenin ((R)-1) compared with the Boltzmann-weighted ECD s...
Figure 5: Structure and population of the low-energy CAM-B3LYP/TZVP PCM/MeCN conformers (>2%) of (2R,5’’R)-2d....
Figure 6: Structure and population of the low-energy CAM-B3LYP/TZVP PCM/MeCN conformers (>2%) of (2R,5’’S)-2a....
Figure 7: Experimental HPLC-ECD spectra of (2R,5’’S)-2a (second eluted stereoisomer) and (2R,5’’R)-2d (fourth...
Figure 8: Experimental HPLC–ECD spectra of (2R,5’’S)-2a and (2R,5’’R)-2d compared with the Boltzmann-weighted...
Figure 9: a) Chiral HPLC–UV and HPLC–ECD traces of dracocephins B1–B4 3a–d using a Chiralpak IC column with t...
Figure 10: Structure and population of the low-energy CAM-B3LYP/TZVP PCM/MeCN conformers (>2%) of (2R,5’’R)-3c....
Figure 11: Structure and population of the low-energy CAM-B3LYP/TZVP PCM/MeCN conformers (>2%) of (2R,5’’S)-3b....
Figure 12: Experimental HPLC-ECD spectra of 3b (first eluted stereoisomer) and 3c (third eluted stereoisomer) ...
Figure 13: Experimental HPLC-ECD spectra of 3b and 3c compared with the Boltzmann-weighted ECD spectra compute...
Figure 14: Proposed mechanism for the formation of dracocephins A and B (2a–d and 3a–d) starting from (±)-9.
Inhibition of peptide aggregation by means of enzymatic phosphorylation
- Kristin Folmert,
- Malgorzata Broncel,
- Hans v. Berlepsch,
- Christopher H. Ullrich,
- Mary-Ann Siegert and
- Beate Koksch
Beilstein J. Org. Chem. 2016, 12, 2462–2470, doi:10.3762/bjoc.12.240
- treatment with 2 mL TFA (trifluoroacetic acid/iPr3SiH/H2O (90:9:1)) for three hours. The resin was washed twice with 1 mL TFA and DCM, and excess of solvent was removed by evaporation. The peptides were precipitated with cold Et2O, pelleted by centrifugation and dried by lyophilization. All peptides were
Graphical Abstract
Scheme 1: Helical wheel projection of two parallel helical strands and primary structure of KFM6. The recogni...
Figure 1: a) Time-dependent CD spectra and b) corresponding CD-minimum plot for random coil (black) and β-she...
Figure 2: ThT-binding assay of of 15 µM KFM6 in 50 mM Tris/HCl buffer with 10 mM MgCl2 at pH 7.5, 24 °C, and ...
Figure 3: a) TEM micrograph of 15 µM KFM6 in 50 mM Tris/HCl buffer with 10 mM MgCl2 at pH 7.5 and 24 °C. The ...
Figure 4: a) Enzymatic phosphorylation of 15 µM KFM6 in time-dependent CD-minimum plots. Addition of both 200...
Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group
- Mikhail Yu. Ievlev,
- Oleg V. Ershov,
- Mikhail Yu. Belikov,
- Angelina G. Milovidova,
- Viktor A. Tafeenko and
- Oleg E. Nasakin
Beilstein J. Org. Chem. 2016, 12, 2093–2098, doi:10.3762/bjoc.12.198
- derivatives 3 we carried out the reaction of specially prepared 6-imino-2,7-dioxabicyclo[3.2.1]octane-3,3,4-tricarbonitrile 3h [21] with dry trifluoroacetic acid under anhydrous conditions (Table 2, entry 6). The successful implementation of this process and isolation of product 2h with good yield indicate
Graphical Abstract
Scheme 1: An exclusive approach to 3,4-dihydro-2H-pyran-4-carboxamides from non-pyran sources.
Scheme 2: Known approach to pyran derivatives based on ketonitriles 1.
Figure 1: The molecular structure of 2a with atom-numbering scheme. Displacement ellipsoids are drawn at the ...
Scheme 3: Plausible reaction pathways for 3,4-dihydro-2H-pyran-4-carbxamides 2 formation.
Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides
- Lena Huck,
- Juan F. González,
- Elena de la Cuesta and
- J. Carlos Menéndez
Beilstein J. Org. Chem. 2016, 12, 1772–1777, doi:10.3762/bjoc.12.166
- acidic conditions either failed to give any reaction at room temperature or afforded complex mixtures when heated. After some experimentation, we finally discovered that treatment of compound 2e with trifluoroacetic acid in dichloromethane at 45 °C gave an excellent yield of the β-trifluoroacetamido-α
- trifluoroacetate liberated in the previous step, to give 6. Alternatively, loss of a molecule of methanol from starting compound 2 would lead to intermediate 5 (see Scheme 3), whose reaction with trifluoroacetic acid would furnish 9. Neber-type chemistry would afford the oxonium species 10, which would finally be
Graphical Abstract
Scheme 1: Summary of the work described in this paper.
Scheme 2: Synthesis of aziridines 2.
Figure 1: NOE effects in compound 2f.
Scheme 3: Mechanistic proposal accounting for the chemo- and diastereoselective formation of aziridines 2.
Scheme 4: Transformation of aziridines 2 into β-trifluoroacetamido-α-ketoamides 6.
Scheme 5: Two mechanistic proposals explaining the formation of compounds 6.
Scheme 6: Transformation of aziridines 2 into vicinal tricarbonyl compounds 11 and transformation of the latt...
Scheme 7: Mechanistic proposal for the transformation of aziridines 2 into compounds 11.
Rearrangements of organic peroxides and related processes
- Ivan A. Yaremenko,
- Vera A. Vil’,
- Dmitry V. Demchuk and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162
- oxidative fragmentation at the bridgehead position of adamantanes 157a,b. The reaction employed the trifluoroperacetic acid (TFPAA)/trifluoroacetic acid (TFAA) system and afforded compounds 158a,b in high yields (Scheme 46) [300]. This method for the insertion of an oxygen atom was applied to the oxidation
Graphical Abstract
Figure 1: The named transformations considered in this review.
Scheme 1: The Baeyer–Villiger oxidation.
Scheme 2: The general mechanism of the peracid-promoted Baeyer–Villiger oxidation.
Scheme 3: General mechanism of the Lewis acid-catalyzed Baeyer–Villiger rearrangement.
Scheme 4: The theoretically studied mechanism of the BV oxidation reaction promoted by H2O2 and the Lewis aci...
Scheme 5: Proton movements in the transition states of the Baeyer–Villiger oxidation.
Scheme 6: The dependence of the course of the Baeyer–Villiger oxidation on the type of O–O-bond cleavage in t...
Scheme 7: The acid-catalyzed Baeyer–Villiger oxidation of cyclic epoxy ketones 22.
Scheme 8: Oxidation of isophorone oxide 29.
Scheme 9: Synthesis of acyl phosphate 32 from acyl phosphonate 31.
Scheme 10: Synthesis of aflatoxin B2 (36).
Scheme 11: The Baeyer–Villiger rearrangement of ketones 37 to lactones 38.
Scheme 12: Synthesis of 3,4-dimethoxybenzoic acid (40) via Baeyer–Villiger oxidation.
Scheme 13: Oxone transforms α,β-unsaturated ketones 43 into vinyl acetates 44.
Scheme 14: The Baeyer–Villiger oxidation of ketones 45 using diaryl diselenide and hydrogen peroxide.
Scheme 15: Baeyer–Villiger oxidation of (E)-2-methylenecyclobutanones.
Scheme 16: Oxidation of β-ionone (56) by H2O2/(BnSe)2 with formation of (E)-2-(2,6,6-trimethylcyclohex-1-en-1-...
Scheme 17: The mechanism of oxidation of ketones 58a–f by hydrogen peroxide in the presence of arsonated polys...
Scheme 18: Oxidation of ketone (58b) by H2O2 to 6-methylcaprolactone (59b) catalyzed by Pt complex 66·BF4.
Scheme 19: Oxidation of ketones 67 with H2O2 in the presence of [(dppb}Pt(µ-OH)]22+.
Scheme 20: The mechanism of oxidation of ketones 67 in the presence of [(dppb}Pt(µ-OH)]22+ and H2O2.
Scheme 21: Oxidation of benzaldehydes 69 in the presence of the H2O2/MeReO3 system.
Scheme 22: Oxidation of acetophenones 72 in the presence of the H2O2/MeReO3 system.
Scheme 23: Baeyer–Villiger oxidation of 2-adamantanone (45c) in the presence of Sn-containing mesoporous silic...
Scheme 24: Aerobic Baeyer–Villiger oxidation of ketones 76 using metal-free carbon.
Scheme 25: A regioselective Baeyer-Villiger oxidation of functionalized cyclohexenones 78 into a dihydrooxepin...
Scheme 26: The oxidation of aldehydes and ketones 80 by H2O2 catalyzed by Co4HP2Mo15V3O62.
Scheme 27: The cleavage of ketones 82 with hydrogen peroxide in alkaline solution.
Scheme 28: Oxidation of ketones 85 to esters 86 with H2O2–urea in the presence of KHCO3.
Scheme 29: Mechanism of the asymmetric oxidation of cyclopentane-1,2-dione 87a with the Ti(OiPr)4/(+)DET/t-BuO...
Scheme 30: The oxidation of cis-4-tert-butyl-2-fluorocyclohexanone (93) with m-chloroperbenzoic acid.
Scheme 31: The mechanism of the asymmetric oxidation of 3-substituted cyclobutanone 96a in the presence of chi...
Scheme 32: Enantioselective Baeyer–Villiger oxidation of cyclic ketones 98.
Scheme 33: Regio- and enantioselective Baeyer–Villiger oxidation of cyclic ketones 101.
Scheme 34: The proposed mechanism of the Baeyer–Villiger oxidation of acetal 105f.
Scheme 35: Synthesis of hydroxy-10H-acridin-9-one 117 from tetramethoxyanthracene 114.
Scheme 36: The Baeyer–Villiger oxidation of the fully substituted pyrrole 120.
Scheme 37: The Criegee rearrangement.
Scheme 38: The mechanism of the Criegee reaction of a peracid with a tertiary alcohol 122.
Scheme 39: Criegee rearrangement of decaline ethylperoxoate 127 into ketal 128.
Scheme 40: The ionic cleavage of 2-methoxy-2-propyl perester 129.
Scheme 41: The Criegee rearrangement of α-methoxy hydroperoxide 136.
Scheme 42: Synthesis of enol esters and acetals via the Criegee rearrangement.
Scheme 43: Proposed mechanism of the transformation of 1-hydroperoxy-2-oxabicycloalkanones 147a–d.
Scheme 44: Transformation of 3-hydroxy-1,2-dioxolanes 151 into diketone derivatives 152.
Scheme 45: Criegee rearrangement of peroxide 153 with the mono-, di-, and tri-O-insertion.
Scheme 46: The sequential Criegee rearrangements of adamantanes 157a,b.
Scheme 47: Synthesis of diaryl carbonates 160a–d from triarylmethanols 159a–d through successive oxygen insert...
Scheme 48: The synthesis of sesquiterpenes 162 from ketone 161 with a Criegee rearrangement as one key step.
Scheme 49: Synthesis of trans-hydrindan derivatives 164, 165.
Scheme 50: The Hock rearrangement.
Scheme 51: The general scheme of the cumene process.
Scheme 52: The Hock rearrangement of aliphatic hydroperoxides.
Scheme 53: The mechanism of solvolysis of brosylates 174a–c and spiro cyclopropyl carbinols 175a–c in THF/H2O2....
Scheme 54: The fragmentation mechanism of hydroperoxy acetals 178 to esters 179.
Scheme 55: The acid-catalyzed rearrangement of phenylcyclopentyl hydroperoxide 181.
Scheme 56: The peroxidation of tertiary alcohols in the presence of a catalytic amount of acid.
Scheme 57: The acid-catalyzed reaction of bicyclic secondary alcohols 192 with hydrogen peroxide.
Scheme 58: The photooxidation of 5,6-disubstituted 3,4-dihydro-2H-pyrans 196.
Scheme 59: The oxidation of tertiary alcohols 200a–g, 203a,b, and 206.
Scheme 60: Transformation of functional peroxide 209 leading to 2,3-disubstitued furans 210 in one step.
Scheme 61: The synthesis of carbazoles 213 via peroxide rearrangement.
Scheme 62: The construction of C–N bonds using the Hock rearrangement.
Scheme 63: The synthesis of moiety 218 from 217 which is a structural motif in the antitumor–antibiotic of CC-...
Scheme 64: The in vivo oxidation steps of cholesterol (219) by singlet oxygen.
Scheme 65: The proposed mechanism of the rearrangement of cholesterol-5α-OOH 220.
Scheme 66: Photochemical route to artemisinin via Hock rearrangement of 223.
Scheme 67: The Kornblum–DeLaMare rearrangement.
Scheme 68: Kornblum–DeLaMare transformation of 1-phenylethyl tert-butyl peroxide (225).
Scheme 69: The synthesis 4-hydroxyenones 230 from peroxide 229.
Scheme 70: The Kornblum–DeLaMare rearrangement of peroxide 232.
Scheme 71: The reduction of peroxide 234.
Scheme 72: The Kornblum–DeLaMare rearrangement of endoperoxide 236.
Scheme 73: The rearrangement of peroxide 238 under Kornblum–DeLaMare conditions.
Scheme 74: The proposed mechanism of rearrangement of peroxide 238.
Scheme 75: The Kornblum–DeLaMare rearrangement of peroxides 242a,b.
Scheme 76: The base-catalyzed rearrangements of bicyclic endoperoxides having electron-withdrawing substituent...
Scheme 77: The base-catalyzed rearrangements of bicyclic endoperoxides 249a,b having electron-donating substit...
Scheme 78: The base-catalyzed rearrangements of bridge-head substituted bicyclic endoperoxides 251a,b.
Scheme 79: The Kornblum–DeLaMare rearrangement of hydroperoxide 253.
Scheme 80: Synthesis of β-hydroxy hydroperoxide 254 from endoperoxide 253.
Scheme 81: The amine-catalyzed rearrangement of bicyclic endoperoxide 263.
Scheme 82: The base-catalyzed rearrangement of meso-endoperoxide 268 into 269.
Scheme 83: The photooxidation of 271 and subsequent Kornblum–DeLaMare reaction.
Scheme 84: The Kornblum–DeLaMare rearrangement as one step in the oxidation reaction of enamines.
Scheme 85: The Kornblum–DeLaMare rearrangement of 3,5-dihydro-1,2-dioxenes 284, 1,2-dioxanes 286, and tert-but...
Scheme 86: The Kornblum–DeLaMare rearrangement of epoxy dioxanes 290a–d.
Scheme 87: Rearrangement of prostaglandin H2 292.
Scheme 88: The synthesis of epicoccin G (297).
Scheme 89: The Kornblum–DeLaMare rearrangement used in the synthesis of phomactin A.
Scheme 90: The Kornblum–DeLaMare rearrangement in the synthesis of 3H-quinazolin-4-one 303.
Scheme 91: The Kornblum–DeLaMare rearrangement in the synthesis of dolabriferol (308).
Scheme 92: Sequential transformation of 3-substituted 2-pyridones 309 into 3-hydroxypyridine-2,6-diones 311 in...
Scheme 93: The Kornblum–DeLaMare rearrangement of peroxide 312 into hydroxy enone 313.
Scheme 94: The Kornblum–DeLaMare rearrangement in the synthesis of polyfunctionalized carbonyl compounds 317.
Scheme 95: The Kornblum–DeLaMare rearrangement in the synthesis of (Z)-β-perfluoroalkylenaminones 320.
Scheme 96: The Kornblum–DeLaMare rearrangement in the synthesis of γ-ketoester 322.
Scheme 97: The Kornblum–DeLaMare rearrangement in the synthesis of diterpenoids 326 and 328.
Scheme 98: The synthesis of natural products hainanolidol (331) and harringtonolide (332) from peroxide 329.
Scheme 99: The synthesis of trans-fused butyrolactones 339 and 340.
Scheme 100: The synthesis of leucosceptroid C (343) and leucosceptroid P (344) via the Kornblum–DeLaMare rearra...
Scheme 101: The Dakin oxidation of arylaldehydes or acetophenones.
Scheme 102: The mechanism of the Dakin oxidation.
Scheme 103: A solvent-free Dakin reaction of aromatic aldehydes 356.
Scheme 104: The organocatalytic Dakin oxidation of electron-rich arylaldehydes 358.
Scheme 105: The Dakin oxidation of electron-rich arylaldehydes 361.
Scheme 106: The Dakin oxidation of arylaldehydes 358 in water extract of banana (WEB).
Scheme 107: A one-pot approach towards indolo[2,1-b]quinazolines 364 from indole-3-carbaldehydes 363 through th...
Scheme 108: The synthesis of phenols 367a–c from benzaldehydes 366a-c via acid-catalyzed Dakin oxidation.
Scheme 109: Possible transformation paths of the highly polarized boric acid coordinated H2O2–aldehyde adduct 3...
Scheme 110: The Elbs oxidation of phenols 375 to hydroquinones.
Scheme 111: The mechanism of the Elbs persulfate oxidation of phenols 375 affording p-hydroquinones 376.
Scheme 112: Oxidation of 2-pyridones 380 under Elbs persulfate oxidation conditions.
Scheme 113: Synthesis of 3-hydroxy-4-pyridone (384) via an Elbs oxidation of 4-pyridone (382).
Scheme 114: The Schenck rearrangement.
Scheme 115: The Smith rearrangement.
Scheme 116: Three main pathways of the Schenck rearrangement.
Scheme 117: The isomerization of hydroperoxides 388 and 389.
Scheme 118: Trapping of dioxacyclopentyl radical 392 by oxygen.
Scheme 119: The hypothetical mechanism of the Schenck rearrangement of peroxide 394.
Scheme 120: The autoxidation of oleic acid (397) with the use of labeled isotope 18O2.
Scheme 121: The rearrangement of 18O-labeled hydroperoxide 400 under an atmosphere of 16O2.
Scheme 122: The rearrangement of the oleate-derived allylic hydroperoxides (S)-421 and (R)-425.
Scheme 123: Mechanisms of Schenck and Smith rearrangements.
Scheme 124: The rearrangement and cyclization of 433.
Scheme 125: The Wieland rearrangement.
Scheme 126: The rearrangement of bis(triphenylsilyl) 439 or bis(triphenylgermyl) 441 peroxides.
Scheme 127: The oxidative transformation of cyclic ketones.
Scheme 128: The hydroxylation of cyclohexene (447) in the presence of tungstic acid.
Scheme 129: The oxidation of cyclohexene (447) under the action of hydrogen peroxide.
Scheme 130: The reaction of butenylacetylacetone 455 with hydrogen peroxide.
Scheme 131: The oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 132: The proposed mechanism for the oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 133: The rearrangement of ozonides.
Scheme 134: The acid-catalyzed oxidative rearrangement of malondialdehydes 462 under the action of H2O2.
Scheme 135: Pathways of the Lewis acid-catalyzed cleavage of dialkyl peroxides 465 and ozonides 466.
Scheme 136: The mechanism of the transformation of (tert-butyldioxy)cyclohexanedienones 472.
Scheme 137: The synthesis of Vitamin K3 from 472a.
Scheme 138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Scheme 139: The rearrangement of hydroperoxide 485 to form diketone 486.
Scheme 140: The base-catalyzed rearrangement of cyclic peroxides 488a–g.
Scheme 141: Synthesis of chiral epoxides and aldols from peroxy hemiketals 491.
Scheme 142: The multistep transformation of (R)-carvone (494) to endoperoxides 496a–e.
Scheme 143: The decomposition of anthracene endoperoxide 499.
Scheme 144: Synthesis of esters 503 from aldehydes 501 via rearrangement of peroxides 502.
Scheme 145: Two possible paths for the base-promoted decomposition of α-azidoperoxides 502.
Scheme 146: The Story decomposition of cyclic diperoxide 506a.
Scheme 147: The Story decomposition of cyclic triperoxide 506b.
Scheme 148: The thermal rearrangement of endoperoxides A into diepoxides B.
Scheme 149: The transformation of peroxide 510 in the synthesis of stemolide (511).
Scheme 150: The possible mechanism of the rearrangement of endoperoxide 261g.
Scheme 151: The photooxidation of indene 517.
Scheme 152: The isomerization of ascaridole (523).
Scheme 153: The isomerization of peroxide 525.
Scheme 154: The thermal transformation of endoperoxide 355.
Scheme 155: The photooxidation of cyclopentadiene (529) at a temperature higher than 0 °C.
Scheme 156: The thermal rearrangement of endoperoxides 538a,b.
Scheme 157: The transformation of peroxides 541.
Scheme 158: The thermal rearrangements of strained cyclic peroxides.
Scheme 159: The thermal rearrangement of diacyl peroxide 551 in the synthesis of C4-epi-lomaiviticin B core 553....
Scheme 160: The 1O2 oxidation of tryptophan (554) and rearrangement of dioxetane intermediate 555.
Scheme 161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Scheme 162: The proposed mechanism of the Fe(II)-promoted rearrangement of 557a–c.
Scheme 163: The reaction of dioxolane 563 with Fe(II) sulfate.
Scheme 164: Fe(II)-promoted rearrangement of 1,2-dioxane 565.
Scheme 165: Fe(II) cysteinate-promoted rearrangement of 1,2-dioxolane 568.
Scheme 166: The transformation of 1,2-dioxanes 572a–c under the action of FeCl2.
Scheme 167: Fe(II) cysteinate-promoted transformation of tetraoxane 574.
Scheme 168: The CoTPP-catalyzed transformation of bicyclic endoperoxides 600a–d.
Scheme 169: The CoTPP-catalyzed transformation of epoxy-1,2-dioxanes.
Scheme 170: The Ru(II)-catalyzed reactions of 1,4-endoperoxide 261g.
Scheme 171: The Ru(II)-catalyzed transformation as a key step in the synthesis of elyiapyrone A (610) from 1,4-...
Scheme 172: Peroxides with antimalarial activity.
Scheme 173: The interaction of iron ions with artemisinin (616).
Scheme 174: The interaction of FeCl2 with 1,2-dioxanes 623, 624.
Scheme 175: The mechanism of reaction 623 and 624 with Fe(II)Cl2.
Scheme 176: The reaction of bicyclic natural endoperoxides G3-factors 631–633 with FeSO4.
Scheme 177: The transformation of terpene cardamom peroxide 639.
Scheme 178: The different ways of the cleavage of tetraoxane 643.
Scheme 179: The LC–MS analysis of interaction of tetraoxane 646 with iron(II)heme 647.
Scheme 180: The rearrangement of 3,6-epidioxy-1,10-bisaboladiene (EDBD, 649).
Scheme 181: Easily oxidized substrates.
Scheme 182: Biopathway of synthesis of prostaglandins.
Scheme 183: The reduction and rearrangements of isoprostanes.
Scheme 184: The partial mechanism for linoleate 658 oxidation.
Scheme 185: The transformation of lipid hydroperoxide.
Scheme 186: The acid-catalyzed cleavage of the product from free-radical oxidation of cholesterol (667).
Scheme 187: Two pathways of catechols oxidation.
Scheme 188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme...
Scheme 189: Carotinoides 679 cleavage by carotenoid cleavage dioxygenases.
Methylpalladium complexes with pyrimidine-functionalized N-heterocyclic carbene ligands
- Dirk Meyer and
- Thomas Strassner
Beilstein J. Org. Chem. 2016, 12, 1557–1565, doi:10.3762/bjoc.12.150
- group uses a mixture of trifluoroacetic acid (TFA) and its anhydride (TFAA) as solvents. It has the advantage that the formed ester can be separated and hydrolyzed, followed by recycling of the free acid which potentially can be reused in the process [24][25][26][27][28][29][30]. Contrary to the
- CDCl3, where two different signals for the m-pyrimidine protons are observed. We recently reported that the dihalogenato complexes are active catalysts of the methane CH activation in trifluoroacetic acid [34]. Under the reaction conditions it seems likely, that an exchange of the chloro against a
- ). We could also confirm the formation of the desired product by a solid state structure (Figure 4). Typical reaction conditions of the catalytic CH activation are 30 atmospheres of methane under strongly oxidizing conditions (potassium peroxodisulfate, trifluoroacetic acid and its anhydride), where
Graphical Abstract
Scheme 1: Synthesis of the monomethylpalladium(II) complexes 9–11 (in DCM) and 12 (in CH3CN).
Figure 1: Possible isomers.
Figure 2: ORTEP [39] style plot of complex 9 in the solid state. Thermal ellipsoids are given at the 50% probabil...
Figure 3: ORTEP [39] style plot of complex 12 in the solid state. Thermal ellipsoids are drawn at the 50% probabi...
Scheme 2: Synthesis of complex 13.
Figure 4: ORTEP [39] style plot of complex 13 in the solid state. Thermal ellipsoids are drawn at the 50% probabi...
Scheme 3: Possible pathways of methyl trifluoroacetate formation starting from complex 13.
Scheme 4: Synthesis of complex 14 by conversion of complex 13 with iodobenzene bistrifluoroacetate.
Scheme 5: Synthesis of the [((pym)^(NHC-R))PdII(CH3)2] complex 15.
Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene
- Shulei Pan,
- Hang Jiang,
- Yanghui Zhang,
- Yu Zhang and
- Dushen Chen
Beilstein J. Org. Chem. 2016, 12, 1302–1308, doi:10.3762/bjoc.12.122
- obtained in 20% yield (Table 5, entry 1). While the yield was improved to 42% in the presence of 2.0 equiv DMSO (Table 5, entry 2), it decreased when 4.0 equiv DMSO were used (Table 5, entry 3). Since the solubility of 1 in trifluoroacetic acid is low, we envisaged that the addition of co-solvents would
Graphical Abstract
Figure 1: Tetraphenylene and its saddle-shaped structure.
Scheme 1: The Pd(OAc)2-catalyzed reaction of nitriles with tetraphenylene (1).
Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates
- Mohammad Haji
Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121
- -phosphonates: A one-pot three-component synthesis of N-arylisoquinolone-1-phosphonates 119 through the Kabachnik–Fields reaction of ethyl 2-(2-formyl-4,5-dimethoxyphenyl)acetate (116) with anilines 117 and triethyl phosphite in the presence of trifluoroacetic acid as catalyst has been reported by Borse et al
Graphical Abstract
Scheme 1: The Biginelli condensation.
Scheme 2: The Biginelli reaction of β-ketophosphonates catalyzed by ytterbium triflate.
Scheme 3: Trimethylchlorosilane-mediated Biginelli reaction of diethyl (3,3,3-trifluoropropyl-2-oxo)phosphona...
Scheme 4: Biginelli reaction of dialkyl (3,3,3-trifluoropropyl-2-oxo)phosphonate with trialkyl orthoformates ...
Scheme 5: p-Toluenesulfonic acid-promoted Biginelli reaction of β-ketophosphonates, aryl aldehydes and urea.
Scheme 6: General Kabachnik–Fields reaction for the synthesis of α-aminophosphonates.
Scheme 7: Phthalocyanine–AlCl catalyzed Kabachnik–Fields reaction of N-Boc-piperidin-4-one with diethyl phosp...
Scheme 8: Kabachnik–Fields reaction of isatin with diethyl phosphite and benzylamine.
Scheme 9: Magnetic Fe3O4 nanoparticle-supported phosphotungstic acid-catalyzed Kabachnik–Fields reaction of i...
Scheme 10: The Mg(ClO4)2-catalyzed Kabachnik–Fields reaction of 1-tosylpiperidine-4-one.
Scheme 11: An asymmetric version of the Kabachnik–Fields reaction for the synthesis of α-amino-3-piperidinylph...
Scheme 12: A classical Kabachnik–Fields reaction followed by an intramolecular ring-closing reaction for the s...
Scheme 13: Synthesis of (S)-piperidin-2-phosphonic acid through an asymmetric Kabachnik–Fields reaction.
Scheme 14: A modified diastereoselective Kabachnik–Fields reaction for the synthesis of isoindolin-1-one-3-pho...
Scheme 15: A microwave-assisted Kabachnik–Fields reaction toward isoindolin-1-ones.
Scheme 16: The synthesis of 3-arylmethyleneisoindolin-1-ones through a Horner–Wadsworth–Emmons reaction of Kab...
Scheme 17: An efficient one-pot method for the synthesis of ethyl (2-alkyl- and 2-aryl-3-oxoisoindolin-1-yl)ph...
Scheme 18: FeCl3 and PdCl2 co-catalyzed three-component reaction of 2-alkynylbenzaldehydes, anilines, and diet...
Scheme 19: Three-component reaction of 6-methyl-3-formylchromone (75) with hydrazine derivatives or hydroxylam...
Scheme 20: Three-component reaction of 6-methyl-3-formylchromone (75) with thiourea, guanidinium carbonate or ...
Scheme 21: Three-component reaction of 6-methyl-3-formylchromone (75) with 1,4-bi-nucleophiles in the presence...
Scheme 22: One-pot three-component reaction of 2-alkynylbenzaldehydes, amines, and diethyl phosphonate.
Scheme 23: Lewis acid–surfactant combined catalysts for the one-pot three-component reaction of 2-alkynylbenza...
Scheme 24: Lewis acid catalyzed cyclization of different Kabachnik–Fields adducts.
Scheme 25: Three-component synthesis of N-arylisoquinolone-1-phosphonates 119.
Scheme 26: CuI-catalyzed three-component tandem reaction of 2-(2-formylphenyl)ethanones with aromatic amines a...
Scheme 27: Synthesis of 1,5-benzodiazepin-2-ylphosphonates via ytterbium chloride-catalyzed three-component re...
Scheme 28: FeCl3-catalyzed four-component reaction for the synthesis of 1,5-benzodiazepin-2-ylphosphonates.
Scheme 29: Synthesis of indole bisphosphonates through a modified Kabachnik–Fields reaction.
Scheme 30: Synthesis of heterocyclic bisphosphonates via Kabachnik–Fields reaction of triethyl orthoformate.
Scheme 31: A domino Knoevenagel/phospha-Michael process for the synthesis of 2-oxoindolin-3-ylphosphonates.
Scheme 32: Intramolecular cyclization of phospha-Michael adducts to give dihydropyridinylphosphonates.
Scheme 33: Synthesis of fused phosphonylpyrans via intramolecular cyclization of phospha-Michael adducts.
Scheme 34: InCl3-catalyzed three-component synthesis of (2-amino-3-cyano-4H-chromen-4-yl)phosphonates.
Scheme 35: Synthesis of phosphonodihydropyrans via a domino Knoevenagel/hetero-Diels–Alder process.
Scheme 36: Multicomponent synthesis of phosphonodihydrothiopyrans via a domino Knoevenagel/hetero-Diels–Alder ...
Scheme 37: One-pot four-component synthesis of 1,2-dihydroisoquinolin-1-ylphosphonates under multicatalytic co...
Scheme 38: CuI-catalyzed four-component reactions of methyleneaziridines towards alkylphosphonates.
Scheme 39: Ruthenium–porphyrin complex-catalyzed three-component synthesis of aziridinylphosphonates and its p...
Scheme 40: Copper(I)-catalyzed three-component reaction towards 1,2,3-triazolyl-5-phosphonates.
Scheme 41: Three-component reaction of acylphosphonates, isocyanides and dialkyl acetylenedicarboxylate to aff...
Scheme 42: Synthesis of (4-imino-3,4-dihydroquinazolin-2-yl)phosphonates via an isocyanide-based three-compone...
Scheme 43: Silver-catalyzed three-component synthesis of (2-imidazolin-4-yl)phosphonates.
Scheme 44: Three-component synthesis of phosphonylpyrazoles.
Scheme 45: One-pot three-component synthesis of 3-carbo-5-phosphonylpyrazoles.
Scheme 46: A one-pot two-step method for the synthesis of phosphonylpyrazoles.
Scheme 47: A one-pot method for the synthesis of (5-vinylpyrazolyl)phosphonates.
Scheme 48: Synthesis of 1H-pyrrol-2-ylphosphonates via the [3 + 2] cycloaddition of phosphonate azomethine yli...
Scheme 49: Three-component synthesis of 1H-pyrrol-2-ylphosphonates.
Scheme 50: The classical Reissert reaction.
Scheme 51: One-pot three-component synthesis of N-phosphorylated isoquinolines.
Scheme 52: One-pot three-component synthesis of 1-acyl-1,2-dihydroquinoline-2-phosphonates and 2-acyl-1,2-dihy...
Scheme 53: Three-component reaction of pyridine derivatives with ethyl propiolate and dialkyl phosphonates.
Scheme 54: Three-component reactions for the phosphorylation of benzothiazole and isoquinoline.
Scheme 55: Three-component synthesis of diphenyl [2-(aminocarbonyl)- or [2-(aminothioxomethyl)-1,2-dihydroisoq...
Scheme 56: Three-component stereoselective synthesis of 1,2-dihydroquinolin-2-ylphosphonates and 1,2-dihydrois...
Scheme 57: Diphosphorylation of diazaheterocyclic compounds via a tandem 1,4–1,2 addition of dimethyl trimethy...
Scheme 58: Multicomponent reaction of alkanedials, acetamide and acetyl chloride in the presence of PCl3 and a...
Scheme 59: An oxidative domino three-component synthesis of polyfunctionalized pyridines.
Scheme 60: A sequential one-pot three-component synthesis of polysubstituted pyrroles.
Scheme 61: Three-component decarboxylative coupling of proline with aldehydes and dialkyl phosphites for the s...
Scheme 62: Three-component domino aza-Wittig/phospha-Mannich sequence for the phosphorylation of isatin deriva...
Scheme 63: Stereoselective synthesis of phosphorylated trans-1,5-benzodiazepines via a one-pot three-component...
Scheme 64: One-pot three-component synthesis of phosphorylated 2,6-dioxohexahydropyrimidines.
Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates
- Jarosław Lewkowski,
- Maria Rodriguez Moya,
- Anna Wrona-Piotrowicz,
- Janusz Zakrzewski,
- Renata Kontek and
- Gabriela Gajek
Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117
- (3Ai) was obtained, when the Kabachnik–Fields reaction was carried out in the presence of a catalytic amount of trifluoroacetic acid in refluxing acetonitrile. The same procedure, i.e., the Kabachnik–Fields reaction in the presence of trifluoroacetic acid, but in refluxing methanol has been
Graphical Abstract
Scheme 1: Synthesis of aminophosphonates 3Aa–j, 3Ba–e, 3Ca–d, 3Cg, aminophosphonic acids 4a, 4c and hydroxyph...
Figure 1: Normalized electronic absorption and emission spectra of 3Aj and pyrene in chloroform (c = 1 μM).
Figure 2: Emission spectra of compound 3Aj in various solvents. The spectra are normalized at ≈378 nm (pyrene...
Figure 3: IC50 values of studied compounds.
A cross-metathesis approach to novel pantothenamide derivatives
- Jinming Guan,
- Matthew Hachey,
- Lekha Puri,
- Vanessa Howieson,
- Kevin J. Saliba and
- Karine Auclair
Beilstein J. Org. Chem. 2016, 12, 963–968, doi:10.3762/bjoc.12.95
- next reaction without further purification due to its low stability. The required amine 14 to be coupled to 13 was synthesized from Boc-protected β-alanine and pentylamine using a method reported by Hoegl et al. [11]. Deprotection of the Boc group with trifluoroacetic acid (TFA) provided the free amine
Graphical Abstract
Figure 1: Chemical structures of N-pentylpantothenamide (1) and of its methyl allyl derivative 2.
Figure 2: Structure of Grubbs’ catalysts used in this study.
Scheme 1: From (R)-malic acid to allyl derivatives 8 and 9 tested in cross-metathesis. Details are provided i...
Scheme 2: Synthesis of compounds 10c and 10d.
Scheme 3: Synthesis of 16.
Figure 3: In vitro antiplasmodial activity of compound 16 in growth medium containing pantetheinase (open sym...
Gold-catalyzed direct alkynylation of tryptophan in peptides using TIPS-EBX
- Gergely L. Tolnai,
- Jonathan P. Brand and
- Jerome Waser
Beilstein J. Org. Chem. 2016, 12, 745–749, doi:10.3762/bjoc.12.74
- modified reaction conditions (10 mol % AuCl(SMe2), three equivalents TIPS-EBX (1a) and 2 mol % trifluoroacetic acid as co-catalyst) [39]. They also demonstrated that the obtained silylalkyne products can be easily deprotected with fluoride sources to allow bioconjugation via cycloaddition with azides
Graphical Abstract
Figure 1: Functionalization of natural peptides and proteins: state of the art.
Scheme 1: Alkynylation with EBX reagents.
Scheme 2: Alkynylation of tryptophan-containing peptides.
Elucidation of a masked repeating structure of the O-specific polysaccharide of the halotolerant soil bacteria Azospirillum halopraeferens Au4
- Elena N. Sigida,
- Yuliya P. Fedonenko,
- Alexander S. Shashkov,
- Nikolay P. Arbatsky,
- Evelina L. Zdorovenko,
- Svetlana A. Konnova,
- Vladimir V. Ignatov and
- Yuriy A. Knirel
Beilstein J. Org. Chem. 2016, 12, 636–642, doi:10.3762/bjoc.12.62
- hydrolysis of the lipopolysaccharide isolated by the phenol–water extraction from the halotolerant soil bacteria Azospirillum halopraeferens type strain Au4. The polysaccharide was studied by sugar and methylation analyses, selective cleavages by Smith degradation and solvolysis with trifluoroacetic acid
Graphical Abstract
Scheme 1: Structures of the OPS from A. halopraeferens Au4 and oligosaccharides obtained from the OPS by Smit...
Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands
- Julia Wappel,
- Roland C. Fischer,
- Luigi Cavallo,
- Christian Slugovc and
- Albert Poater
Beilstein J. Org. Chem. 2016, 12, 154–165, doi:10.3762/bjoc.12.17
- stirred methanol and dried. Noteworthy, hydrochloric acid is the only acid which activates the preinitiators under investigation. Addition of other acids (or acid liberating reagents) such as acetyl chloride or trifluoroacetic acid, were not able to promote the polymerization. Also the addition of
Graphical Abstract
Scheme 1: Synthesis of 1-4; only the isolated and characterized complexes are shown.
Figure 1: Solid state structure of complexes 2a and 2b as retrieved from single crystal X-ray diffraction.
Figure 2: Time/conversion plot for the polymerization of 5 by preinitiators 1–4 in the presence of HCl ([5]:[...
Figure 3: 1H NMR spectrum in the low-field region of the active species for complexes 4 and M32.
Scheme 2: Energetics of 2a and 2b protonation in kcal/mol.
Figure 4: Reaction pathway of the transformation of 2b to HovII (energies in kcal/mol; main distances in Å).
Figure 5: DTA-TGA measurements for polymerizations of DCPD with catalysts 1b and 2b; Reaction conditions: [ca...
Diastereoselective Ugi reaction of chiral 1,3-aminoalcohols derived from an organocatalytic Mannich reaction
- Samantha Caputo,
- Andrea Basso,
- Lisa Moni,
- Renata Riva,
- Valeria Rocca and
- Luca Banfi
Beilstein J. Org. Chem. 2016, 12, 139–143, doi:10.3762/bjoc.12.15
- , by additional crystallization, affording these key intermediates in high ee and de (syn relative configuration, see Supporting Information File 1). The tert-butyl urethane was then deblocked with trifluoroacetic acid. Neutralization and extraction afforded crude aminoalcohols 5a–e, that were directly
Graphical Abstract
Scheme 1: Overall strategy.
Scheme 2: Boc-protected aminoalcohols used as inputs in a diastereoselective Ugi reaction.
Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines
- Brett N. Hemric and
- Qiu Wang
Beilstein J. Org. Chem. 2016, 12, 22–28, doi:10.3762/bjoc.12.4
- efficiencies were observed in the reactions with more acidic benzoic acids, indicating a correlation of their reactivity to their acidity which remains to be further clarified [44]. Furthermore, when trifluoroacetic acid was employed as an oxygen source, the free 1,2-amino alcohol 4g was isolated, possibly due
Graphical Abstract
Figure 1: Examples of valuable 1,2-oxyamino-containing molecules.
Scheme 1: Strategies for intermolecular olefin oxyamination.
Scheme 2: Examples of carboxylic acids in the olefin oxyamination reaction. Reaction conditions: 1 (1.2 mmol,...
Scheme 3: Examples of O-benzoylhydroxylamines in the olefin oxyamination reaction. Reaction conditions: 1a (1...
Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane
- Mohammed Salah Ayoup,
- David B. Cordes,
- Alexandra M. Z. Slawin and
- David O'Hagan
Beilstein J. Org. Chem. 2015, 11, 2671–2676, doi:10.3762/bjoc.11.287
- trifluoroacetic acid (TFA) or 6 M HCl in dioxane [10] gave the corresponding benzoic acids 11, 12, and 13 as illustrated in Scheme 1. Direct palladium catalysed formylation of aryl iodides 6/7 as a mixture was explored using Pd(PPh3)4, Bu4SnH and CO [11]. This generated benzaldehyde derivatives 14 and 15 in a 1:3
Graphical Abstract
Figure 1: All cis-hexafluoro- 1 and tetrafluorocyclohexanes 2 and 3 result in facially polarised ring motifs ...
Scheme 1: Preparation of benzoic acids 11–13; i. HIO4·2H2O (50%), AcOH, H2SO4, I2, H2O, 70 °C 24 h, 92%.; ii....
Scheme 2: Synthesis of benzaldehyde derivatives 14 and 15: i. Pd(PPh3)4, Bu3SnH, THF, CO (1 atm), 50 °C, 2–3 ...
Figure 2: X-ray structure of aldehyde 15. CCDC number 1432193.
Scheme 3: Olefination reactions of 15 and the X-ray structure of 17 (CCDC number 1432194): i. Zn, TiCl4, THF,...
Scheme 4: Reactions from aldehyde 15: i. NaBH4, THF, 20 °C, 1 h, 98%.; ii. HI (57%), CHCl3, 30 h, 95%; iii. Bu...
Scheme 5: Reactions of benzyl azide 21; i. 24, Cu(OAc)2, Na ascorbate, t-BuOH, H2O, 20 °C, 16 h, 72%; ii. HCl...
Scheme 6: Reactions of aldehyde 14: i. NaBH4, THF, rt, 1 h, 98%.; ii. HI (57%), CHCl3, 30 h, 94%; iii. Bu4NN3...
Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations
- Tsuyuka Sugiishi,
- Hideki Amii,
- Kohsuke Aikawa and
- Koichi Mikami
Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286
- microreactor, a new protocol for scalable aromatic trifluoromethylation was developed. From a mechanistic aspect, Vicic and co-workers explored the direct generation of CF3Cu from CF3CO2Cu. The use of (N-heterocyclic carbene)copper-trifluoroacetates prepared from trifluoroacetic acid (TFA) was investigated in
- , such as perfluoroalkyl acetates, trifluoroacetic acid, chlorodifluoroacetates, trifluoromethyl ketones and hemiaminals of trifluoroacetaldehyde, are attractive perfluoroalkyl anion sources for aromatic perfluoroalkylation reactions. The generation of perfluoroalkylcopper from perfluoroalkyl carboxylic
- determined by 19F NMR analysis using CF3CH2OH as an internal standard. C–H trifluoromethylation of arenes using trifluoroacetic acid. CF3Cu generated from chlorofluoroacetate and CuI. [18F]Trifluoromethyation with difluorocarbenes for PET. aRadiochemical yield determined by HPLC. Trifluoromethylation with
Graphical Abstract
Scheme 1: Trifluoromethylation using trifluoroacetate.
Scheme 2: Decarboxylative pentafluoroethylation and its application.
Scheme 3: Trifluoromethyation with trifluoroacetate in a flow system.
Scheme 4: Trifluoromethylation of 4-bromotoluene by [(NHC)Cu(TFA)].
Scheme 5: Trifluoromethylation of aryl iodides with small amounts of Cu and Ag2O. aThe yield was determined b...
Scheme 6: C–H trifluoromethylation of arenes using trifluoroacetic acid.
Scheme 7: CF3Cu generated from chlorofluoroacetate and CuI.
Scheme 8: [18F]Trifluoromethyation with difluorocarbenes for PET. aRadiochemical yield determined by HPLC.
Scheme 9: Trifluoromethylation with trifluoroacetate and copper iodide.
Scheme 10: Preparation of trifluoromethylcopper from trifluoromethyl ketone.
Scheme 11: Trifluoromethylation of aryl iodides. aIsolated yield. b1 equivalent each of CF3Cu reagent and 1,10...
Scheme 12: Pentafluoroethylation of aryl bromides. aYield was determined by 19F NMR analysis using benzotriflu...
Scheme 13: Perfluoroalkylation reactions of arylboronic acids. aIsolated yield. bDMF was used instead of tolue...
Scheme 14: Trifluoromethylation with silylated hemiaminal of fluoral.
Scheme 15: Catalytic trifluoromethylation with a fluoral derivative.
Scheme 16: The scope of Cu-catalyzed aromatic trifluoromethylation. The yield was determined by 19F NMR analys...
Scheme 17: Plausible mechanism of Cu-catalyzed aromatic trifluoromethylation [53].
Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition
- Nicolas Desbois,
- Sandrine Pacquelet,
- Adrien Dubois,
- Clément Michelin and
- Claude P. Gros
Beilstein J. Org. Chem. 2015, 11, 2202–2208, doi:10.3762/bjoc.11.239
- trifluoroacetic acid, followed by oxidation under the action of DDQ. Cu and Ga complexes were prepared by the strategy outlined in Scheme 2. The insertion of Cu into corrole 1 was easily achieved with Cu(OAc)2·H2O in THF during 15 min. To obtain the gallium corrole 8b, free-base azidocorrole 1 was dissolved in a
- first dissolved in trifluoroacetic acid (TFA) and stirred at room temperature overnight. A brown oil was obtained upon concentration. The residue was then purified by flash chromatography. Chelation of Cu2+ with propargyl NOTA 4 was performed in aqueous solution by Cu(ClO4)2·6H2O. Purification of Cu
Graphical Abstract
Figure 1: Selected ligands for the copper(I)-catalyzed Huisgen cycloaddition.
Scheme 1: Structure of different bimetallic complexes 5–7.
Scheme 2: Synthesis of 8a,b and 9a–d. (i) for 8a: THF, N2, Cu(OAc)2·H2O, rt 15 min; for 8b: GaCl3 0.114 M in ...
Scheme 3: Synthesis of 10a,b and 12a,b. (i) For 10a: Milli-Q water, Gd(NO3)3·5H2O, 50 °C, 17 h, pH 8.0; for 1...
Investigation on the reactivity of α-azidochalcones with carboxylic acids: Formation of α-amido-1,3-diketones and highly substituted 2-(trifluoromethyl)oxazoles
- Kandasamy Rajaguru,
- Arumugam Mariappan,
- Rajendran Suresh,
- Periasamy Manivannan and
- Shanmugam Muthusubramanian
Beilstein J. Org. Chem. 2015, 11, 2021–2028, doi:10.3762/bjoc.11.219
- Abstract The reaction of α-azidochalcones with carboxylic acids has been investigated resulting in the formation of α-amido-1,3-diketones under microwave irradiation via in situ formation of 2H-azirine intermediates. An interesting reaction is described wherein, with trifluoroacetic acid at lower
- two steps following a literature procedure [29]. Results and Discussion The investigation was initiated by treating α-azidochalcone 1a (R1 = 4-Br, R2 = 4-OMe) with trifluoroacetic acid (2a). This acid was allowed to react with the azidochalcone at room temperature for 30 minutes and a low yield of 3a
- -azidochalcone 1a (R1 = 4-Br, R2 = 4-OMe) with trifluoroacetic acid under microwave conditions [33] at 100 °C for 2 minutes to obtain diketone 3a (79%) as a solid without any side products (Scheme 1). The 1H NMR spectrum of 3a exhibits a methine proton doublet at 6.78 ppm. In the 13C NMR spectrum, two carbonyl
Graphical Abstract
Figure 1: Formation of substituted aziridine.
Figure 2: Various strategies for the formation of 2H-azirine.
Scheme 1: Attempted reaction for the synthesis of 3a.
Figure 3: Synthesis of α-amido-1,3-diketone (3a–o). Reaction conditions: α-azidochalcone 1 (1.0 equiv) and ca...
Scheme 2: Plausible mechanism.
Scheme 3: Attempted reaction with acid derivatives.
Scheme 4: Oxazole formation from 3.
Figure 4: Possible isomers for 7.
Scheme 5: Oxazole formation.
Figure 5: Synthesis of highly substituted 2-(trifluoromethyl)oxazoles (8a–e). Reaction conditions: α-azidocha...
Scheme 6: Mechanism for the formation of 8.
Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand
- Thibault E. Schmid,
- Florian Modicom,
- Adrien Dumas,
- Etienne Borré,
- Loic Toupet,
- Olivier Baslé and
- Marc Mauduit
Beilstein J. Org. Chem. 2015, 11, 1541–1546, doi:10.3762/bjoc.11.169
- , we proceeded to synthesize complex 4b, featuring the 5-bromo-2-picolinate moiety. Using a similar methodology, the desired complex was obtained with 42% yield. The activation of the new picolinic complex 4a was initially evaluated in the presence of trifluoroacetic acid (TFA), a Brønsted acid easy to
Graphical Abstract
Scheme 1: Synthesis of [NHC(picolinate)RuCl(indenylidene)] complexes 2 and 4a.
Scheme 2: Synthesis of complex 4a and 4b from (SIPr)(pyridine)RuCl2(indenylidene) (5).
Figure 1: Solid-state structure of complex 4a from single crystal X-ray diffraction. Hydrogens have been omit...
Figure 2: Olefin metathesis profiles in response to TFA equivalents.
Figure 3: Comparison of olefin metathesis profiles for catalysts 2, 4a and 4b after activation with 150 equiv...
Figure 4: Influence of various acids for the activation of 4a in the RCM of DEDAM.
Synthesis and evaluation of the biostability and cell compatibility of novel conjugates of nucleobase, peptidic epitope, and saccharide
- Dan Yuan,
- Xuewen Du,
- Junfeng Shi,
- Ning Zhou,
- Abdulgader Ahmed Baoum,
- Khalid Omar Al Footy,
- Khadija Omar Badahdah and
- Bing Xu
Beilstein J. Org. Chem. 2015, 11, 1352–1359, doi:10.3762/bjoc.11.145
- chain from the resin with 95% trifluoroacetic acid (TFA) without N-protecting groups. Later, NAS was obtained by reacting D-glucosamine hydrochloride with the fully protected NA. After cleaving the protecting group on amino acids with 95% TFA, we used reversed-phase high-performance liquid
Graphical Abstract
Scheme 1: Chemical structures of the conjugates (nucleobase–amino acids–saccharide (NAS)), and nucleopeptides...
Scheme 2: The representative synthesis route of conjugates NAS (1, including solid-phase peptide synthesis an...
Figure 1: TEM images of (A) solution of 1 + 8; (B) hydrogel of 5 + 8; (C) solution of 7 + 8. Each component i...
Figure 2: (A) Strain sweep and (B) frequency sweep of the solution of 1 + 8, the hydrogel of 5 + 8, and the s...
Figure 3: Compounds remained after incubating with proteinase K (3.2 U/mL) for 24 h at 37 °C. (A) Each conjug...
Figure 4: Cell viability of HeLa cells incubated with (A) 1, (B) 2, (C) 3, (D) 4, (E) 5, (F) 6, (G) 7, (H) 8 ...
Figure 5: Cell viability of PC12 cells incubated with (A) 1, (B) 2, (C) 3, (D) 4, (E) 5, (F) 6, (G) 7, (H) 8 ...
Figure 6: Cell viability of (A) HeLa and (B) PC12 cells incubated with 5 + 8 at different concentrations.
Selected synthetic strategies to cyclophanes
- Sambasivarao Kotha,
- Mukesh E. Shirbhate and
- Gopalkrushna T. Waghule
Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142
- with trifluoroacetic acid (TFA) in the presence of pentamethylbenzene to generate mycocyclosin (135, 74%) (Scheme 19). Wurtz coupling: The Wurtz reaction is one of the oldest methods to form a C–C bond in organic synthesis. Baker and co-workers [138] have reported the synthesis of cyclophanes 137 and
- acetylenedicarboxylate (DMAD) to deliver compounds 332a,b (77%). These DA adducts were irradiated in diethyl ether/dichloromethane (5:1) to offer the corresponding bioxaquadricyclane 333, subsequent thermolysis gave the bioxepine 334 (81%). Finally, aromatization of bioxepine 334 with trifluoroacetic acid (TFA
Graphical Abstract
Figure 1: General representation of cyclophanes.
Figure 2: cyclophanes one or more with heteroatom.
Figure 3: Metathesis catalysts 12–17 and C–C coupling catalyst 18.
Figure 4: Natural products containing the cyclophane skeleton.
Figure 5: Turriane family of natural products.
Scheme 1: Synthesis of [3]ferrocenophanes through Mannich reaction. Reagents and conditions: (i) excess HNMe2...
Scheme 2: Synthesis of cyclophanes through Michael addition. Reagents and conditions: (i) xylylene dibromide,...
Scheme 3: Synthesis of normuscopyridine analogue 37 through an oxymercuration–oxidation strategy. Reagents an...
Scheme 4: Synthesis of tribenzocyclotriyne 39 through Castro–Stephens coupling reaction. Reagents and conditi...
Scheme 5: Synthesis of cyclophane 43 through Glaser–Eglinton coupling. Reagents and conditions: (i) 9,10-bis(...
Scheme 6: Synthesis of the macrocyclic C-glycosyl cyclophane through Glaser coupling. Reagents and conditions...
Scheme 7: Synthesis of cyclophane-containing complex 49 through Glaser–Eglinton coupling reaction. Reagents a...
Scheme 8: Synthesis of cyclophane 53 through Glaser–Eglinton coupling. Reagents and conditions: (i) K2CO3, ac...
Figure 6: Cyclophanes 54–56 that have been synthesized through Glaser–Eglinton coupling.
Figure 7: Synthesis of tetrasubstituted [2.2]paracyclophane 57 and chiral cyclophyne 58 through Eglinton coup...
Scheme 9: Synthesis of cyclophane through Glaser–Hay coupling reaction. Reagents and conditions: (i) CuCl2 (1...
Scheme 10: Synthesis of seco-C/D ring analogs of ergot alkaloids through intramolecular Heck reaction. Reagent...
Scheme 11: Synthesis of muscopyridine 73 via Kumada coupling. Reagents and conditions: (i) 72, THF, ether, 20 ...
Scheme 12: Synthesis of the cyclophane 79 via McMurry coupling. Reagents and conditions: (i) 75, decaline, ref...
Scheme 13: Synthesis of stilbenophane 81 via McMurry coupling. Reagents and conditions: (i) TiCl4, Zn, pyridin...
Scheme 14: Synthesis of stilbenophane 85 via McMurry coupling. Reagents and conditions: (i) NBS (2 equiv), ben...
Figure 8: List of cyclophanes prepared via McMurry coupling reaction as a key step.
Scheme 15: Synthesis of paracyclophane by cross coupling involving Pd(0) catalyst. Reagents and conditions: (i...
Scheme 16: Synthesis of the cyclophane 112 via the pinacol coupling and 113 by RCM. Reagents and conditions: (...
Scheme 17: Synthesis of cyclophane derivatives 122a–c via Sonogoshira coupling. Reagents and conditions: (i) C...
Scheme 18: Synthesis of cyclophane 130 via Suzuki–Miyaura reaction as a key step. Reagents and conditions: (i)...
Scheme 19: Synthesis of the mycocyclosin via Suzuki–Miyaura cross coupling. Reagents and conditions: (i) benzy...
Scheme 20: Synthesis of cyclophanes via Wurtz coupling reaction Reagents and conditions: (i) PhLi, Et2O, C6H6,...
Scheme 21: Synthesis of non-natural glycophanes using alkyne metathesis. Reagents and conditions: (i) G-I (12)...
Figure 9: Synthesis of cyclophanes via ring-closing alkyne metathesis.
Scheme 22: Synthesis of crownophanes by cross-enyne metathesis. Reagents and conditions: (i) G-II (13), 5 mol ...
Scheme 23: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 24: Synthesis of cyclophane 159 derivatives via SM cross-coupling and RCM. Reagents and conditions: (i)...
Scheme 25: Sexithiophene synthesis via cross metathesis. Reagents and conditions: (i) 161, Pd(PPh3)4, K2CO3, T...
Scheme 26: Synthesis of pyrrole-based cyclophane using enyne metathesis. Reagents and conditions: (i) Se, chlo...
Scheme 27: Synthesis of macrocyclic derivatives by RCM. Reagents and conditions: (i) G-I/G-II, CH2Cl2, 0.005 M...
Scheme 28: Synthesis of enantiopure β-lactam-based dienyl bis(dihydrofuran) 179. Reagents and conditions: (i) ...
Scheme 29: Synthesis of a [1.1.6]metaparacyclophane derivative 183 via SM cross coupling. Reagents and conditi...
Scheme 30: Synthesis of a [1.1.6]metaparacyclophane derivative 190 via SM cross coupling. Reagents and conditi...
Scheme 31: Template-promoted synthesis of cyclophanes involving RCM. Reagents and conditions: (i) acenaphthene...
Scheme 32: Synthesis of [3.4]cyclophane derivatives 200 via SM cross coupling and RCM. Reagents and conditions...
Figure 10: Examples for cyclophanes synthesized by RCM.
Scheme 33: Synthesis of the longithorone C framework assisted by fluorinated auxiliaries. Reagents and conditi...
Scheme 34: Synthesis of the longithorone framework via RCM. Reagents and conditions: (i) 213, NaH, THF, rt, 10...
Scheme 35: Synthesis of floresolide B via RCM as a key step. Reagents and conditions: (i) G-II (13, 0.1 equiv)...
Scheme 36: Synthesis of normuscopyridine (223) by the RCM strategy. Reagents and condition: (i) Mg, THF, hexen...
Scheme 37: Synthesis of muscopyridine (73) via RCM. Reagents and conditions: (i) 225, NaH, THF, 0 °C to rt, 1....
Scheme 38: Synthesis of muscopyridine (73) via RCM strategy. Reagents and conditions: (i) NaH, n-BuLi, 5-bromo...
Scheme 39: Synthesis of pyridinophane derivatives 223 and 245. Reagents and conditions: (i) PhSO2Na, TBAB, CH3...
Scheme 40: Synthesis of metacyclophane derivatives 251 and 253. Reagents and conditions: (i) 240, NaH, THF, rt...
Scheme 41: Synthesis of normuscopyridine and its higher analogues. Reagents and conditions: (i) alkenyl bromid...
Scheme 42: Synthesis of fluorinated ferrocenophane 263 via a [2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 43: Synthesis of [2.n]metacyclophanes 270 via a [2 + 2] cycloaddition. Reagents and conditions: (i) Ac2...
Scheme 44: Synthesis of metacyclophane 273 by a [2 + 2 + 2] co-trimerization. Reagents and conditions: (i) [Rh...
Scheme 45: Synthesis of paracyclophane 276 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: ...
Scheme 46: Synthesis of cyclophane 278 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: (i) ...
Scheme 47: Synthesis of cyclophane 280 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) [(Rh(cod)(...
Scheme 48: Synthesis of taxane framework by a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) Cp(CO)2 ...
Scheme 49: Synthesis of cyclophane 284 and 285 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditio...
Scheme 50: Synthesis of pyridinophanes 293a,b and 294a,b via a [2 + 2 + 2] cycloaddition. Reagents and conditi...
Scheme 51: Synthesis of pyridinophanes 296 and 297 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 52: Synthesis of triazolophane by a 1,3-dipolar cycloaddition. Reagents and conditions: (i) propargyl b...
Scheme 53: Synthesis of glycotriazolophane 309 by a click reaction. Reagents and conditions: (i) LiOH, H2O, Me...
Figure 11: Cyclophanes 310 and 311 prepared via click chemistry.
Scheme 54: Synthesis of cyclophane via the Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C, 12 h...
Scheme 55: Synthesis of [6,6]metacyclophane by a Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C...
Scheme 56: Synthesis of cyclophanes by a Dötz benzannulation. Reagents and conditions: (i) THF, 65 °C, 3 h; (i...
Scheme 57: Synthesis of muscopyridine (73) via an intramolecular DA reaction of ketene. Reagents and condition...
Scheme 58: Synthesis of bis[10]paracyclophane 336 via Diels–Alder reaction. Reagents and conditions: (i) DMAD,...
Scheme 59: Synthesis of [8]paracyclophane via DA reaction. Reagents and conditions: (i) maleic anhydride, 3–5 ...
Scheme 60: Biomimetic synthesis of (−)-longithorone A. Reagents and conditions: (i) Me2AlCl, CH2Cl2, −20 °C, 7...
Scheme 61: Synthesis of sporolide B (349) via a [4 + 2] cycloaddition reaction. Reagents and conditions: (i) P...
Scheme 62: Synthesis of the framework of (+)-cavicularin (352) via a [4 + 2] cycloaddition. Reagents and condi...
Scheme 63: Synthesis of oxazole-containing cyclophane 354 via Beckmann rearrangement. Reagents and conditions:...
Scheme 64: Synthesis of cyclophanes 360a–c via benzidine rearrangement. Reagents and conditions: (i) 356a–d, K2...
Scheme 65: Synthesis of cyclophanes 365a–c via benzidine rearrangement. Reagents and conditions: (i) BocNHNH2,...
Scheme 66: Synthesis of metacyclophane 367 via Ciamician–Dennstedt rearrangement. Reagents and conditions: (i)...
Scheme 67: Synthesis of cyclophane by tandem Claisen rearrangement and RCM as key steps. Reagents and conditio...
Scheme 68: Synthesis of cyclophane derivative 380. Reagents and conditions: (i) K2CO3, CH3CN, allyl bromide, r...
Scheme 69: Synthesis of metacyclophane via Cope rearrangement. Reagents and conditions: (i) MeOH, NaBH4, rt, 1...
Scheme 70: Synthesis of cyclopropanophane via Favorskii rearrangement. Reagents and conditions: (i) Br2, CH2Cl2...
Scheme 71: Cyclophane 389 synthesis via photo-Fries rearrangement. Reagents and conditions: (i) DMAP, EDCl/CHCl...
Scheme 72: Synthesis of normuscopyridine (223) via Schmidt rearrangement. Reagents and conditions: (i) ethyl s...
Scheme 73: Synthesis of crownophanes by tandem Claisen rearrangement. Reagents and conditions: (i) diamine, Et3...
Scheme 74: Attempted synthesis of cyclophanes via tandem Claisen rearrangement and RCM. Reagents and condition...
Scheme 75: Synthesis of muscopyridine via alkylation with 2,6-dimethylpyridine anion. Reagents and conditions:...
Scheme 76: Synthesis of cyclophane via Friedel–Craft acylation. Reagents and conditions: (i) CS2, AlCl3, 7 d, ...
Scheme 77: Pyridinophane 418 synthesis via Friedel–Craft acylation. Reagents and conditions: (i) 416, AlCl3, CH...
Scheme 78: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) NBS, A...
Scheme 79: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) BEMP, ...
Scheme 80: Cyclophane synthesis by coupling with TosMIC. Reagents and conditions: (i) (a) ClCH2OCH3, TiCl4, CS2...
Scheme 81: Synthesis of diaza[32]cyclophanes and triaza[33]cyclophanes. Reagents and conditions: (i) DMF, NaH,...
Scheme 82: Synthesis of cyclophane 439 via acyloin condensation. Reagents and conditions: (i) Na, xylene, 75%;...
Scheme 83: Synthesis of multibridged binuclear cyclophane 442 by aldol condensation. Reagents and conditions: ...
Scheme 84: Synthesis of various macrolactones. Reagents and conditions: (i) iPr2EtN, DMF, 77–83%; (ii) TBDMSCl...
Scheme 85: Synthesis of muscone and muscopyridine via Yamaguchi esterification. Reagents and conditions: (i) 4...
Scheme 86: Synthesis of [5]metacyclophane via a double elimination reaction. Reagents and conditions: (i) LiBr...
Figure 12: Cyclophanes 466–472 synthesized via Hofmann elimination.
Scheme 87: Synthesis of cryptophane via Baylis–Hillman reaction. Reagents and conditions: (i) methyl acrylate,...
Scheme 88: Synthesis of cyclophane 479 via double Chichibabin reaction. Reagents and conditions: (i) excess 478...
Scheme 89: Synthesis of cyclophane 483 via double Chichibabin reaction. Reagents and conditions: (i) 481, OH−;...
Scheme 90: Synthesis of cyclopeptide via an intramolecular SNAr reaction. Reagents and conditions: (i) TBAF, T...
Scheme 91: Synthesis of muscopyridine (73) via C-zip ring enlargement reaction. Reagents and conditions: (i) H...
Figure 13: Mechanism of the formation of compound 494.
Scheme 92: Synthesis of indolophanetetraynes 501a,b using the Nicholas reaction as a key step. Reagents and co...
Scheme 93: Synthesis of cyclophane via radical cyclization. Reagents and conditions: (i) cyclododecanone, phen...
Scheme 94: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 95: Cyclophane synthesis via Wittig reaction. Reagents and conditions: (i) LiOEt (2.1 equiv), THF, −78 ...
Figure 14: Representative examples of cyclophanes synthesized via Wittig reaction.
Scheme 96: Synthesis of the [6]paracyclophane via isomerization of Dewar benzene. Reagents and conditions: (i)...
