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Search for "trichloromethyl group" in Full Text gives 4 result(s) in Beilstein Journal of Organic Chemistry.
Highly electrophilic, gem- and spiro-activated trichloromethylnitrocyclopropanes: synthesis and structure
- Ilia A. Pilipenko,
- Mikhail V. Grigoriev,
- Olga Yu. Ozerova,
- Igor A. Litvinov,
- Darya V. Spiridonova,
- Aleksander V. Vasilyev and
- Sergey V. Makarenko
Beilstein J. Org. Chem. 2026, 22, 123–130, doi:10.3762/bjoc.22.5
- carboxylic acids [4]. The trichloromethyl group is a convenient precursor of the carboxylic function, which determines their use in the synthesis of α-amino acids [5]. A number of natural trichloromethyl-containing compounds are metabolites of symbionts of marine sponges – cyanobacteria [6][7][8] – and have
- cyclopropane ring is probably a consequence of the formation of a sterically hindered carbanion II in a conformation with an anti-periplanar position of the bulky substituents – bromine and a trichloromethyl group (Scheme 6). Due to the steric reasons, the anion in this conformation is selectively protonated
- , benzoylacetonitrile), spirocarbo- (based on 1,3-indanedione) and spiroheterocyclic (based on Meldrum's acid, dimethylbarbituric acid, 3-methyl-1-phenyl-5-pyrazolone) cyclopropane structures were isolated and characterized. Keywords: bromonitropropene; CH-acids; cyclopropanes; nitrocyclopropanes; trichloromethyl
Graphical Abstract
Figure 1: Two natural trichloromethyl-containing compounds.
Scheme 1: Approaches to the synthesis of vic-trifluoromethylnitrocyclopropanes.
Scheme 2: Synthesis of monocyclic trichloromethylnitrocyclopropanes 2–5.
Scheme 3: Synthesis of spiro-fused trichloromethylnitrocyclopropane 6.
Scheme 4: Synthesis of spiro-fused trichloromethylnitrocyclopropanes 7–9. i: 1.5 AcOK, MeOH, rt, 3 h.
Scheme 5: Main NOE correlations in 9a, 9b.
Scheme 6: Proposed mechanism of the formation of trichloromethylnitrocyclopropanes.
Figure 2: Geometry of 2 in the crystal.
Figure 3: Geometry of 3 in the crystal.
Figure 4: Geometry of 9a in the crystal.
Figure 5: Geometry of 9b in the crystal.
Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps
- Ignaz Betcke,
- Alissa C. Götzinger,
- Maryna M. Kornet and
- Thomas J. J. Müller
Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178
- -phenyl-2,4-hexanedione was generated in situ through acid hydrolysis of 1,1,1-trichloro-4-methoxy-6-phenyl-3-hexen-2-ones 71. Subsequent cyclization with hydrazine hydrochloride followed by hydrolysis of the trichloromethyl group led to 73. This intermediate was then reacted with 2,2,2-trifluoroethanol
Graphical Abstract
Scheme 1: Consecutive three-component synthesis of pyrazoles 1 via in situ-formed 1,3-diketones 2 [44].
Scheme 2: Consecutive three-component synthesis of 4-ethoxycarbonylpyrazoles 5 via SmCl3-catalyzed acylation ...
Scheme 3: Consecutive four-component synthesis of 1-(thiazol-2-yl)pyrazole-3-carboxylates 8 [51].
Scheme 4: Three-component synthesis of thiazolylpyrazoles 17 via in situ formation of acetoacetylcoumarins 18 ...
Scheme 5: Consecutive pseudo-four-component and four-component synthesis of pyrazoles 21 from sodium acetylac...
Scheme 6: Consecutive three-component synthesis of 1-substituted pyrazoles 24 from boronic acids, di(Boc)diim...
Scheme 7: Consecutive three-component synthesis of N-arylpyrazoles 25 via in situ formation of aryl-di(Boc)hy...
Scheme 8: Consecutive three-component synthesis of 1,3,4-substituted pyrazoles 27 and 28 from methylhydrazine...
Scheme 9: Consecutive three-component synthesis of 4-allylpyrazoles 32 via oxidative allylation of 1,3-dicarb...
Scheme 10: Pseudo-five-component synthesis of tris(pyrazolyl)methanes 35 [61].
Scheme 11: Pseudo-three-component synthesis of 5-(indol-3-yl)pyrazoles 39 from 1,3,5-triketones 38 [64].
Scheme 12: Three-component synthesis of thiazolylpyrazoles 43 [65].
Scheme 13: Three-component synthesis of triazolo[3,4-b]-1,3,4-thiadiazin-3-yl substituted 5-aminopyrazoles 47 [67]....
Scheme 14: Consecutive three-component synthesis of 5-aminopyrazoles 49 via formation of β-oxothioamides 50 [68].
Scheme 15: Synthesis of 3,4-biarylpyrazoles 52 from aryl halides, α-bromocinnamaldehyde, and tosylhydrazine vi...
Scheme 16: Consecutive three-component synthesis of 3,4-substituted pyrazoles 57 from iodochromones 55 by Suzu...
Scheme 17: Pseudo-four-component synthesis of pyrazolyl-2-pyrazolines 59 by ring opening/ring closing cyclocon...
Scheme 18: Consecutive three-component synthesis of pyrazoles 61 [77].
Scheme 19: Three-component synthesis of pyrazoles 62 from malononitrile, aldehydes, and hydrazines [78-90].
Scheme 20: Four-component synthesis of pyrano[2,3-c]pyrazoles 63 [91].
Scheme 21: Three-component synthesis of persubstituted pyrazoles 65 from aldehydes, β-ketoesters, and hydrazin...
Scheme 22: Three-component synthesis of pyrazol-4-carbodithioates 67 [100].
Scheme 23: Regioselective three-component synthesis of persubstituted pyrazoles 68 catalyzed by ionic liquid [...
Scheme 24: Consecutive three-component synthesis of 4-halopyrazoles 69 and anellated pyrazoles 70 [102].
Scheme 25: Three-component synthesis of 2,2,2-trifluoroethyl pyrazole-5-carboxylates 72 [103].
Scheme 26: Synthesis of pyrazoles 75 in a one-pot process via carbonylative Heck coupling and subsequent cycli...
Scheme 27: Copper-catalyzed three-component synthesis of 1,3-substituted pyrazoles 76 [105].
Scheme 28: Pseudo-three-component synthesis of bis(pyrazolyl)methanes 78 by ring opening-ring closing cyclocon...
Scheme 29: Three-component synthesis of 1,4,5-substituted pyrazoles 80 [107].
Scheme 30: Consecutive three-component synthesis of 3,5-bis(fluoroalkyl)pyrazoles 83 [111].
Scheme 31: Consecutive three-component synthesis of difluoromethanesulfonyl-functionalized pyrazole 88 [114].
Scheme 32: Consecutive three-component synthesis of perfluoroalkyl-substituted fluoropyrazoles 91 [115].
Scheme 33: Regioselective consecutive three-component synthesis of 1,3,5-substituted pyrazoles 93 [116].
Scheme 34: Three-component synthesis of pyrazoles 96 mediated by trimethyl phosphite [117].
Scheme 35: One-pot synthesis of pyrazoles 99 via Liebeskind–Srogl cross-coupling/cyclocondensation [118].
Scheme 36: Synthesis of 1,3,5-substituted pyrazoles 101 via domino condensation/Suzuki–Miyaura cross-coupling ...
Scheme 37: Consecutive three-component synthesis of 1,3,5-trisubstituted pyrazoles 102 and 103 by Sonogashira ...
Scheme 38: Polymer analogous consecutive three-component synthesis of pyrazole-based polymers 107 [132].
Scheme 39: Synthesis of 1,3,5-substituted pyrazoles 108 by sequentially Pd-catalyzed Kumada–Sonogashira cycloc...
Scheme 40: Consecutive four-step one-pot synthesis of 1,3,4,5-substituted pyrazoles 110 [137].
Scheme 41: Four-component synthesis of pyrazoles 113, 115, and 117 via Sonogashira coupling and subsequent Suz...
Scheme 42: Consecutive four- or five-component synthesis for the preparation of 4-pyrazoly-1,2,3-triazoles 119...
Scheme 43: Four-component synthesis of pyrazoles 121 via alkynone formation by carbonylative Pd-catalyzed coup...
Scheme 44: Preparation of 3-azulenyl pyrazoles 124 by glyoxylation, decarbonylative Sonogashira coupling, and ...
Scheme 45: Four-component synthesis of a 3-indoloylpyrazole 128 [147].
Scheme 46: Two-step synthesis of 5-acylpyrazoles 132 via glyoxylation-Stephen–Castro sequence and subsequent c...
Scheme 47: Copper on iron mediated consecutive three-component synthesis of 3,5-substituted pyrazoles 136 [150].
Scheme 48: Consecutive three-component synthesis of 3-substituted pyrazoles 141 by Sonogashira coupling and su...
Scheme 49: Consecutive three-component synthesis of pyrazoles 143 initiated by Cu(I)-catalyzed carboxylation o...
Scheme 50: Consecutive three-component synthesis of benzamide-substituted pyrazoles 146 starting from N-phthal...
Scheme 51: Consecutive three-component synthesis of 1,3,5-substituted pyrazoles 148 [156].
Scheme 52: Three-component synthesis of 4-ninhydrin-substituted pyrazoles 151 [158].
Scheme 53: Consecutive four-component synthesis of 4-(oxoindol)-1-phenylpyrazole-3-carboxylates 155 [159].
Scheme 54: Three-component synthesis of pyrazoles 160 [160].
Scheme 55: Consecutive three-component synthesis of pyrazoles 165 [162].
Scheme 56: Consecutive three-component synthesis of 3,5-disubstituted and 3-substituted pyrazoles 168 and 169 ...
Scheme 57: Three-component synthesis of 3,4,5-substituted pyrazoles 171 via 1,3-dipolar cycloaddition of vinyl...
Scheme 58: Three-component synthesis of pyrazoles 173 and 174 from aldehydes, tosylhydrazine, and vinylidene c...
Scheme 59: Three-component synthesis of pyrazoles 175 from glyoxyl hydrates, tosylhydrazine, and electron-defi...
Scheme 60: Pseudo-four-component synthesis of pyrazoles 177 from glyoxyl hydrates, tosylhydrazine, and aldehyd...
Scheme 61: Consecutive three-component synthesis of pyrazoles 179 via Knoevenagel-cycloaddition sequence [179].
Scheme 62: Three-component synthesis of 5-dimethylphosphonate substituted pyrazoles 182 from aldehydes, the Be...
Scheme 63: Consecutive three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 185 from al...
Scheme 64: Three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 187 from aldehydes, the...
Scheme 65: Three-component synthesis of 5-diethylphosphonate/5-phenylsulfonyl substituted pyrazoles 189 from a...
Scheme 66: Pseudo-three-component synthesis of 3-(dimethyl phosphonate)-substituted pyrazoles 190 [185].
Scheme 67: Three-component synthesis of 3-trifluoromethylpyrazoles 193 [186].
Scheme 68: Consecutive three-component synthesis of 5-stannyl-substituted 4-fluoropyrazole 197 [191,192].
Scheme 69: Pseudo-three-component synthesis of 3,5-diacyl-4-arylpyrazoles 199 [195].
Scheme 70: Three-component synthesis of pyrazoles 204 via nitrilimines [196].
Scheme 71: Three-component synthesis of 1,3,5-substituted pyrazoles 206 via formation of nitrilimines and sali...
Scheme 72: Pseudo four-component synthesis of pyrazoles 209 from acetylene dicarboxylates 147, hydrazonyl chlo...
Scheme 73: Consecutive three-component synthesis of pyrazoles 213 via syndnones 214 [200].
Scheme 74: Consecutive three-component synthesis of pyrazoles 216 via in situ-formed diazomethinimines 217 [201].
Scheme 75: Consecutive three-component synthesis of 3-methylthiopyrazoles 219 from aldehydes, hydrazine, and 1...
Scheme 76: Three-component synthesis of 1,3,5-substituted pyrazoles 220 from aldehydes, hydrazines, and termin...
Scheme 77: Three-component synthesis of 1,3,4,5-substituted pyrazoles 222 from aldehydes, hydrazines, and DMAD ...
Scheme 78: Pseudo three-component synthesis of pyrazoles 224 from sulfonyl hydrazone and benzyl acrylate under...
Scheme 79: Titanium-catalyzed consecutive four-component synthesis of pyrazoles 225 via enamino imines 226 [211]. a...
Scheme 80: Titanium-catalyzed three-component synthesis of pyrazoles 227 via enhydrazino imine complex interme...
Scheme 81: Pseudo-three-component synthesis of pyrazoles 229 via Glaser coupling of terminal alkynes and photo...
Scheme 82: Copper(II)acetate-mediated three-component synthesis of pyrazoles 232 [216].
Scheme 83: Copper-catalyzed three-component synthesis of 1,3,4-substituted pyrazole 234 from oxime acetates, a...
Scheme 84: Three-component synthesis of 3-trifluoroethylpyrazoles 239 [218].
Scheme 85: Pseudo-three-component synthesis of 1,4-bisulfonyl-substituted pyrazoles 242 [219].
Scheme 86: Three-component synthesis of 4-hydroxypyrazole 246 [221].
Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid
- Vladislav A. Sokolov,
- Andrei A. Golushko,
- Irina A. Boyarskaya and
- Aleksander V. Vasilyev
Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105
- ; indanones; trichloromethyl group; triflic acid; Introduction Superelectrophilic activation of organic compounds under the action of strong Brønsted and Lewis acids is an effective method for the synthesis of various carbocycles and heterocycles, and polyfunctional compounds (see books [1][2] and reviews [3
- form of the starting compound [Cl3CCH=CHC(=OH+)Me]. The presence of two strong electron-withdrawing substituents, the trichloromethyl group (CCl3) and a protonated carbonyl (C(OH+)Me), at the carbon–carbon double bond makes this O-protonated species electrophilic enough to react with arenes (Scheme 1a
Graphical Abstract
Scheme 1: Generation of O-protonated and O,C-diprotonated species from substituted conjugated enones under su...
Scheme 2: Synthesis of 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones 1a–o by condensation of acetophenones wit...
Scheme 3: Synthesis of 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones 1p–v by acylation of electron-donating ar...
Scheme 4: Synthesis of 1-aryl-4,4,4-trichlorobut-2-en-1-ones 2 by dehydration of hydroxy ketones 1.
Scheme 5: Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones 2 into 3-trichloromethylindan-1-ones 3 in TfOH....
Scheme 6: Cyclization of 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones 1 into 3-trichloromethylindan-1-ones 3 ...
Scheme 7: Plausible mechanisms for the cyclization of compounds 1 and 2 into indanones 3 in TfOH.
Unexpected rearrangements and a novel synthesis of 1,1-dichloro-1-alkenones from 1,1,1-trifluoroalkanones with aluminium trichloride
- Beatrice Lansbergen,
- Catherine S. Meister and
- Michael C. McLeod
Beilstein J. Org. Chem. 2021, 17, 404–409, doi:10.3762/bjoc.17.36
- trifluoromethyl to a trichloromethyl group with AlCl3 has been previously reported [30][31][32], investigations into the analogous transformation of aliphatic CF3 groups has been limited to adamantly-trifluoromethyl moieties [33][34]. An NMR analysis of the crude product mixture obtained using our original
Graphical Abstract
Figure 1: Examples of biologically active 1,1-dichloro-1-alkenes.
Figure 2: a) Common methods for the preparation of 1,1-dichloro-1-alkenes from aldehydes. b) This work: a two...
Scheme 1: The initial attempt for the conversion of 1,1,1-trifluoroalkanone 5a to 1,1-dichloroalkenone 6a.
Scheme 2: Substrate scope for the reaction of 1,1,1 trifluoroalkanones with AlCl3. aPurification (normal or r...
Scheme 3: Proposed mechanism for the formation of dichloroalkene 6 from trifluoroalkanone 5.
Scheme 4: Formation of bicyclic ketones 9 and 10 from 1,1,1-trifluoroalkanone 5b using 7 equivalents of AlCl3....
Scheme 5: Conversion of 1,1,1-trifluoroalkanone 5n to acid chloride 13 with AlCl3, and possible mechanism.
Scheme 6: Conversion of 1,1,1-trifluoroalkane 16 to bicycle 17 upon treatment with AlCl3, and possible mechan...
