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Search for "diastereoselective fluorination" in Full Text gives 3 result(s) in Beilstein Journal of Organic Chemistry.
Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups
- Xiaowei Li,
- Xiaolin Shi,
- Xiangqian Li and
- Dayong Shi
Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218
- diastereoselectivities. Based on the PIP auxiliary developed by Shi, Ge’s group [48] developed a similar direct, highly site- and diastereoselective fluorination of aliphatic amides (Scheme 11b). Although the roles of Fe(OAc)2 and Ag2CO3 were unclear, their addition significantly improved the reaction yield. A catalytic
Graphical Abstract
Scheme 1: The main three strategies of fluorination: nucleophilic, electrophilic and radical fluorination.
Scheme 2: Doyle’s Pd-catalyzed fluorination of allylic chlorides.
Scheme 3: Allylic fluorination of 2- and 3-substituted propenyl esters.
Scheme 4: Regioselective allylic fluorination of cinnamyl phosphorothioate esters.
Scheme 5: Palladium-catalyzed aliphatic C–H fluorination reported by Doyle.
Scheme 6: Pd-catalyzed enantioselective fluorination of α-ketoesters followed by stereoselective reduction to...
Scheme 7: Pd-catalyzed C(sp3)–H fluorination of oxindoles.
Scheme 8: C–H fluorination of 8-methylquinoline derivatives with F− reagents.
Scheme 9: Fluorination of α-cyano acetates reported by van Leeuwen.
Scheme 10: The catalytic enantioselective electrophilic C–H fluorination of α-chloro-β-keto phosphonates.
Scheme 11: Fluorination of unactivated C(sp3)–H bonds directed by the bidentate PIP auxiliary.
Scheme 12: Fluorination of C(sp3)–H bonds at the β-position of carboxylic acids.
Scheme 13: Enantioselective benzylic C–H fluorination with a chiral transient directing group.
Scheme 14: Microwave-heated Pd-catalyzed fluorination of aryl alcohols.
Scheme 15: Fluorination of aryl potassium trifluoroborates.
Scheme 16: C(sp2)–F bond formation using precatalyst [L·Pd]2(cod).
Scheme 17: Pd-catalyzed fluorination of (hetero)aryl triflates and bromides.
Scheme 18: The Pd-catalyzed C–H fluorination of arenes with Selectfluor/NFSI.
Scheme 19: Pd(II)-catalyzed ortho-monofluorination protocol for benzoic acids.
Scheme 20: Pd-catalyzed C(sp2)–H bond fluorination of 2-arylbenzothiazoles.
Scheme 21: Nitrate-promoted fluorination of aromatic and olefinic C(sp2)–H bonds and proposed mechanism.
Scheme 22: Fluorination of oxalyl amide-protected benzylamine derivatives.
Scheme 23: C–H fluorination of benzaldehydes with orthanilic acids as transient directing group.
Scheme 24: Pd(II)-catalyzed aryl C–H fluorination with various directing groups.
Scheme 25: Cu-catalyzed aliphatic, allylic, and benzylic fluorination.
Scheme 26: Cu-catalyzed SN2 fluorination of primary and secondary alkyl bromides.
Scheme 27: Copper-catalyzed fluorination of alkyl triflates.
Scheme 28: Cu-catalyzed fluorination of allylic bromides and chlorides.
Scheme 29: Synthetic strategy for the fluorination of active methylene compounds.
Scheme 30: Fluorination of β-ketoesters using a tartrate-derived bidentate bisoxazoline-Cu(II) complex.
Scheme 31: Highly enantioselective fluorination of β-ketoesters and N-Boc-oxindoles.
Scheme 32: Amide group-assisted site-selective fluorination of α-bromocarbonyl compounds.
Scheme 33: Cu-mediated aryl fluorination reported by Sanford [77].
Scheme 34: Mono- or difluorination reactions of benzoic acid derivatives.
Scheme 35: Cu-catalyzed fluorination of diaryliodonium salts with KF.
Scheme 36: Copper(I)-catalyzed cross-coupling of 2-pyridylaryl bromides.
Scheme 37: AgNO3-catalyzed decarboxylative fluorination of aliphatic carboxylic acids.
Scheme 38: The Mn-catalyzed aliphatic and benzylic C–H fluorination.
Scheme 39: Iron(II)-promoted C–H fluorination of benzylic substrates.
Scheme 40: Ag-catalyzed fluorodecarboxylation of carboxylic acids.
Scheme 41: Vanadium-catalyzed C(sp3)–H fluorination.
Scheme 42: AgNO3-catalyzed radical deboronofluorination of alkylboronates and boronic acids.
Scheme 43: Selective heterobenzylic C–H fluorination with Selectfluor reported by Van Humbeck.
Scheme 44: Fe(II)-catalyzed site-selective fluorination guided by an alkoxyl radical.
Scheme 45: Fluorination of allylic trichloroacetimidates reported by Nguyen et al.
Scheme 46: Iridium-catalyzed fluorination of allylic carbonates with TBAF(t-BuOH)4.
Scheme 47: Iridium-catalyzed asymmetric fluorination of allylic trichloroacetimidates.
Scheme 48: Cobalt-catalyzed α-fluorination of β-ketoesters.
Scheme 49: Nickel-catalyzed α-fluorination of various α-chloro-β-ketoesters.
Scheme 50: Ni(II)-catalyzed enantioselective fluorination of oxindoles and β-ketoesters.
Scheme 51: Scandium(III)-catalyzed asymmetric C–H fluorination of unprotected 3-substituted oxindoles.
Scheme 52: Iron-catalyzed directed C–H fluorination.
Scheme 53: Electrophilic silver-catalyzed Ar–F bond-forming reaction from arylstannanes.
Figure 1: Nucleophilic, electrophilic and radical CF3 sources.
Scheme 54: Cu(I)-catalyzed allylic trifluoromethylation of unactivated terminal olefins.
Scheme 55: Direct copper-catalyzed trifluoromethylation of allylsilanes.
Scheme 56: Cupper-catalyzed enantioselective trifluoromethylation of five and six-membered ring β-ketoesters.
Scheme 57: Cu-catalyzed highly stereoselective trifluoromethylation of secondary propargyl sulfonates.
Scheme 58: Remote C(sp3)–H trifluoromethylation of carboxamides and sulfonamides.
Scheme 59: Trifluoromethylation of allylsilanes with photoredox catalysis.
Scheme 60: Ag-catalyzed decarboxylative trifluoromethylation of aliphatic carboxylic acids in aqueous CH3CN.
Scheme 61: Decarboxylative trifluoromethylation of aliphatic carboxylic acids via combined photoredox and copp...
Scheme 62: Palladium-catalyzed Ar–CF3 bond-forming reaction.
Scheme 63: Palladium-catalyzed trifluoromethylation of arenes with diverse heterocyclic directing groups.
Scheme 64: Pd-catalyzed trifluoromethylation of indoles as reported by Liu.
Scheme 65: Pd-catalyzed trifluoromethylation of vinyl triflates and vinyl nonaflates.
Scheme 66: Pd(II)-catalyzed ortho-trifluoromethylation of aromatic C–H bonds.
Scheme 67: Visible-light-induced Pd(OAc)2-catalyzed ortho-trifluoromethylation of acetanilides with CF3SO2Na.
Scheme 68: CuI-catalyzed trifluoromethylation of aryl- and alkenylboronic acids.
Scheme 69: Cu-catalyzed trifluoromethylation of aryl- and vinylboronic acids.
Scheme 70: Copper-catalyzed trifluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 71: Formation of C(sp2)–CF3 bond catalyzed by copper(I) complex.
Scheme 72: Loh’s Cu(I)-catalyzed trifluoromethylation of enamides and electron-deficient alkenes.
Scheme 73: Copper and iron-catalyzed decarboxylative tri- and difluoromethylation.
Scheme 74: Cu-catalyzed trifluoromethylation of hydrazones developed by Bouyssi.
Scheme 75: Cu(I)-catalyzed trifluoromethylation of terminal alkenes.
Scheme 76: Cu/Ag-catalyzed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 77: Copper-catalyzed direct alkenyl C–H trifluoromethylation.
Scheme 78: Copper(I/II)-catalyzed direct trifluoromethylation of styrene derivatives.
Scheme 79: Regioselective trifluoromethylation of pivalamido arenes and heteroarenes.
Scheme 80: Synthesis of trifluoromethylquinones in the presence of copper(I).
Scheme 81: Oxidative trifluoromethylation of imidazoheterocycles in ionic liquid/water.
Scheme 82: A mild and fast continuous-flow trifluoromethylation of coumarins using a CuI/CF3SO2Na/TBHP system.
Scheme 83: Copper-catalyzed oxidative trifluoromethylation of various 8-aminoquinolines.
Scheme 84: PA-directed copper-catalyzed trifluoromethylation of anilines.
Scheme 85: Trifluoromethylation of potassium vinyltrifluoroborates catalyzed by Fe(II).
Scheme 86: Alkenyl trifluoromethylation catalyzed by Ru(phen)3Cl2 as photocatalyst.
Scheme 87: Ru-catalyzed trifluoromethylation of alkenes by Akita’s group.
Scheme 88: Ir-catalyzed Cvinyl–CF3 bond formation of α,β-unsaturated carboxylic acids.
Scheme 89: Ag(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes.
Scheme 90: Photocatalyzed direct trifluoromethylation of aryl and heteroaryl C–H bonds.
Scheme 91: Rhenium (MTO)-catalyzed direct trifluoromethylation of aromatic substrates.
Scheme 92: Trifluoromethylation of unprotected anilines under [Ir(ppy)3] catalyst.
Scheme 93: Oxidative trifluoromethylation of imidazopyridines and imidazoheterocycles.
Scheme 94: Ruthenium-catalyzed trifluoromethylation of (hetero)arenes with trifluoroacetic anhydride.
Scheme 95: Phosphovanadomolybdic acid-catalyzed direct C–H trifluoromethylation.
Scheme 96: Picolinamide-assisted ortho-trifluoromethylation of arylamines.
Scheme 97: A nickel-catalyzed C–H trifluoromethylation of free anilines.
Scheme 98: Cu-mediated trifluoromethylation of terminal alkynes reported by Qing.
Scheme 99: Huang’s C(sp)–H trifluoromethylation using Togni’s reagent.
Scheme 100: Cu-catalyzed methods for trifluoromethylation with Umemoto’s reagent.
Scheme 101: The synthesis of alkynyl-CF3 compounds in the presence of fac-[Ir(ppy)3] under visible-light irradi...
Scheme 102: Pd-catalyzed Heck reaction reported by Reutrakul.
Scheme 103: Difluoromethylation of enamides and ene-carbamates.
Scheme 104: Difluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 105: Copper-catalyzed direct C(sp2)–H difluoroacetylation reported by Pannecoucke and co-workers.
Scheme 106: Difluoroalkylation of aldehyde-derived hydrazones with functionalized difluoromethyl bromides.
Scheme 107: Photoredox-catalyzed C–H difluoroalkylation of aldehyde-derived hydrazones.
Scheme 108: Synergistic ruthenium(II)-catalyzed C–H difluoromethylation reported by Ackermann.
Scheme 109: Visible-light photocatalytic decarboxylation of α,β-unsaturated carboxylic acids.
Scheme 110: Synthesis of difluorinated ketones via S-alkyl dithiocarbamates obtained from acyl chlorides and po...
Scheme 111: Synthesis of aryl and heteroaryl difluoromethylated phosphonates.
Scheme 112: Difluoroalkylation of secondary propargyl sulfonates using Cu as the catalyst.
Scheme 113: Ru(II)-mediated para-selective difluoromethylation of anilides and their derivatives.
Scheme 114: Bulky diamine ligand promoted cross-coupling of difluoroalkyl bromides.
Scheme 115: Copper-catalyzed C3–H difluoroacetylation of quinoxalinones.
Scheme 116: Copper(I) chloride-catalyzed trifluoromethylthiolation of enamines, indoles and β-ketoesters.
Scheme 117: Copper-boxmi-catalyzed asymmetric trifluoromethylthiolation of β-ketoesters.
Scheme 118: Direct Cu-catalyzed trifluoromethylthiolation of boronic acids and alkynes.
Scheme 119: Cu-catalyzed synthesis of α-trifluoromethylthio-substituted ketones.
Scheme 120: Trifluoromethylthiolation reactions promoted by diazotriflone and copper.
Scheme 121: Halide activation of N-(trifluoromethylthio)phthalimide.
Scheme 122: The visible light-promoted trifluoromethylthiolation reported by Glorius.
Scheme 123: Synthesis of α-trifluoromethylthioesters via Goossen’s approach.
Scheme 124: Photoinduced trifluoromethylthiolation of diazonium salts.
Scheme 125: Ag-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids.
Scheme 126: Catalytic (hetero)aryl C–H trifluoromethoxylation under visible light.
Scheme 127: Photoinduced C–H-bond trifluromethoxylation of (hetero)arenes.
The selective electrochemical fluorination of S-alkyl benzothioate and its derivatives
- Shunsuke Kuribayashi,
- Tomoyuki Kurioka,
- Shinsuke Inagi,
- Ho-Jung Lu,
- Biing-Jiun Uang and
- Toshio Fuchigami
Beilstein J. Org. Chem. 2018, 14, 389–396, doi:10.3762/bjoc.14.27
- be the most suitable combination as electrolytic solvent and supporting salt as well as fluorine source for the anodic fluorination. The electrochemical fluorination of cyclic benzothioates such as benzothiophenone was also achieved. Keywords: anodic cyclization; diastereoselective fluorination
Graphical Abstract
Figure 1: Cyclic voltammograms of 0.1 M Bu4NBF4/MeCN with a Pt disk working electrode in the absence (brown l...
Figure 2: Calculated HOMO diagram of 1a.
Figure 3: Calculated HOMO diagrams of 1h, 1i and 1j.
Scheme 1: Plausible reaction paths of the anodic oxidation of 1i in Et4NF·4HF/CH2Cl2.
Scheme 2: Anodic fluorination of 1k.
Scheme 3: Anodic fluorination of cyclic derivative 1l.
Scheme 4: Anodic oxidation of 1m and 1n in Et4NF·4HF/CH2Cl2.
Scheme 5: General reaction mechanism for the anodic fluorination of 1.
Scheme 6: Reaction mechanism for the anodic oxidation of carboxylic acids 1m and 1n in the presence of a fluo...
Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules
- Thilo Focken and
- Stephen Hanessian
Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195
- -monofluoroalkylphosphonic acids were synthesized by diastereoselective fluorination of phosphonamides bearing (−)-ephedrine as chiral auxiliary, originally introduced by Sting and Steglich for the synthesis of aminoalkylphosphonic acids [7] (Scheme 16). Thus, condensation of the phosphonic acid dichloride obtained from
Graphical Abstract
Figure 1: Examples of phosphonamide reagents used in stereoselective synthesis.
Figure 2: Natural products and bioactive molecules synthesized using phosphonamide-based chemistry (atoms, bo...
Scheme 1: Olefination with cyclic phosphonamide anions, mechanistic rationale, and selected examples 27a–d [18].
Scheme 2: Asymmetric olefination with chiral phosphonamide anions and selected examples 31a–d [1,22].
Scheme 3: Synthesis of α-substituted phosphonic acids 33a–e by asymmetric alkylation of chiral phosphonamide ...
Scheme 4: Asymmetric conjugate additions of C2-symmetric chiral phosphonamide anions to cyclic enones, lacton...
Scheme 5: Asymmetric conjugate additions of P-chiral phosphonamide anions generated from 40a and 44a to cycli...
Scheme 6: Asymmetric cyclopropanation with chiral chloroallyl phosphonamide 47, mechanistic rationale, and se...
Scheme 7: Asymmetric cyclopropanation with chiral chloromethyl phosphonamide 28d [59].
Scheme 8: Stereoselective synthesis of cis-aziridines 57 from chiral chloroallyl phosphonamide 47a [62].
Scheme 9: Synthesis of phosphonamides by (A) Arbuzov reaction, (B) condensation of diamines with phosphonic a...
Figure 3: Original and revised structure of polyoxin A (69) [24-26].
Scheme 10: Synthesis of (E)-polyoximic acid (9) [24-26].
Figure 4: Key assembly strategy of acetoxycrenulide (10) [41,42].
Scheme 11: Total synthesis of (+)-acetoxycrenulide (10) [41,42].
Scheme 12: Synthesis squalene synthase inhibitor 19 by asymmetric sulfuration (A) and asymmetric alkylation (B...
Figure 5: Key assembly strategy of fumonisin B2 (20) and its tricarballylic acid fragment 105 [45,46].
Scheme 13: Final steps of the total synthesis of fumonisin B2 (20) [45,46].
Figure 6: Selected examples of two subclasses of β-lactam antibiotics – carbapenems (111 and 112) and trinems...
Scheme 14: Synthesis of tricyclic β-lactam antibiotic 123 [97].
Scheme 15: Total synthesis of (−)-anthoplalone (8) [56].
Figure 7: Protein tyrosine phosphatase (PTP) inhibitors 130, 131 and model compounds 16, 132 and 133 [68].
Scheme 16: Synthesis of model PTP inhibitors 16a,b [68].
Scheme 17: Synthesis of aziridine hydroxamic acid 17 as MMP inhibitor [63].
Scheme 18: Synthesis of methyl jasmonate (11) [48].
Figure 8: Structures of nudiflosides A (137) and D (13) [49].
Scheme 19: Total synthesis of the pentasubstituted cyclopentane core 159 of nudiflosides A (151) and D (13) an...
Figure 9: L-glutamic acid (161) and constrained analogues [57,124].
Scheme 20: Stereoselective synthesis of DCG-IV (162) [57].
Scheme 21: Stereoselective synthesis of mGluR agonist 21 [124].
Figure 10: Key assembly strategy of berkelic acid (15) [43].
Scheme 22: Total synthesis of berkelic acid (15) [43].
Figure 11: Key assembly strategy of jerangolid A (22) and ambruticin S (14) [27,28].
Scheme 23: Final assembly steps in the total synthesis of jerangolid A [27].
Scheme 24: Key assembly steps in the total synthesis of ambruticin S (14) [28].
Figure 12: General steroid construction strategy based on conjugate addition of 212 to cyclopentenone 48, exem...
Scheme 25: Total synthesis of estrone (12) [44].
