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Search for "trifluoroethoxy" in Full Text gives 9 result(s) in Beilstein Journal of Organic Chemistry.
Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview
- Louis Monsigny,
- Floriane Doche and
- Tatiana Besset
Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35
- advances have been made for the formation of a C(sp2)–OCHRCF3 bond by transition-metal-catalyzed C–H bond activation. Indeed, fluorinated ethers [71][141][142][143][144][145][146][147][148][149][150][151][152][153] are key compounds, with especially molecules substituted with the 2,2,2-trifluoroethoxy
Graphical Abstract
Scheme 1: Transition-metal-catalyzed C–XRF bond formation by C–H bond activation: an overview.
Scheme 2: Cu(OAc)2-promoted mono- and ditrifluoromethylthiolation of benzamide derivatives derived from 8-ami...
Scheme 3: Trifluoromethylthiolation of azacalix[1]arene[3]pyridines using copper salts and a nucleophilic SCF3...
Scheme 4: Working hypothesis for the palladium-catalyzed C–H trifluoromethylthiolation reaction.
Scheme 5: Trifluoromethylthiolation of 2-arylpyridine derivatives and analogs by means of palladium-catalyzed...
Scheme 6: C(sp2)–SCF3 bond formation by Pd-catalyzed C–H bond activation using AgSCF3 and Selectfluor® as rep...
Scheme 7: Palladium-catalyzed ortho-trifluoromethylthiolation of 2-arylpyridine derivatives reported by the g...
Scheme 8: Palladium-catalyzed ortho-trifluoromethylthiolation of 2-arylpyridine and analogs reported by Anbar...
Scheme 9: Mono- and ditrifluoromethylthiolation of benzamide derivatives derived from 8-aminoquinoline using ...
Scheme 10: Regioselective Cp*Rh(III)-catalyzed directed trifluoromethylthiolation reported by the group of Li [123]...
Scheme 11: Cp*Co(III)-catalyzed ortho-trifluoromethylthiolation of 2-phenylpyridine and 2-phenylpyrimidine der...
Scheme 12: Cp*Co(III)-catalyzed ortho-trifluoromethylthiolation of 2-phenylpyridine and 6-phenylpurine derivat...
Scheme 13: Diastereoselective trifluoromethylthiolation of acrylamide derivatives derived from 8-aminoquinolin...
Scheme 14: C(sp3)–SCF3 bond formation on aliphatic amide derivatives derived from 8-aminoquinoline by palladiu...
Scheme 15: Regio- and diastereoselective difluoromethylthiolation of acrylamides under palladium catalysis rep...
Scheme 16: Palladium-catalyzed (ethoxycarbonyl)difluoromethylthiolation reaction of 2-(hetero)aryl and 2-(α-ar...
Scheme 17: Pd(II)-catalyzed trifluoromethylselenolation of benzamides derived from 5-methoxy-8-aminoquinoline ...
Scheme 18: Pd(II)-catalyzed trifluoromethylselenolation of acrylamide derivatives derived from 5-methoxy-8-ami...
Scheme 19: Transition-metal-catalyzed dehydrogenative 2,2,2-trifluoroethoxylation of (hetero)aromatic derivati...
Scheme 20: Pd(II)-catalyzed ortho-2,2,2-trifluoroethoxylation of N-sulfonylbenzamides reported by the group of...
Scheme 21: Pd(II)-catalyzed selective 2,2,2-trifluoroethoxylation and other fluoroalkoxylations of naphthalene...
Scheme 22: Pd(II)-catalyzed selective ortho-2,2,2-trifluoroethoxylation of benzaldehyde derivatives by means o...
Scheme 23: Pd(II)-catalyzed selective ortho-2,2,2-trifluoroethoxylation (and other fluoroalkoxylations) of ben...
Scheme 24: Pd(II)-catalyzed selective 2,2,2-trifluoroethoxylation of aliphatic amides using a bidentate direct...
Progress in the total synthesis of inthomycins
- Bidyut Kumar Senapati
Beilstein J. Org. Chem. 2021, 17, 58–82, doi:10.3762/bjoc.17.7
- -butylstannyl)ethene (47) using catalytic Pd2dba3 in refluxing THF to produce iodide 48 in 46% yield. The coupling partner (Z,E)-(+)-54 was prepared enatioselectively from the known (E)-3-(tributylstannyl)propenal (49) [46] using a four-step sequence. Treatment of 49 with the Still–Gennari bis-trifluoroethoxy
Graphical Abstract
Figure 1: The inthomycins A–C (1–3) and structurally closely related compounds.
Figure 2: Syntheses of inthomycins A–C (1–3).
Scheme 1: The first total synthesis of racemic inthomycin A (rac)-1 by Whiting.
Scheme 2: Moloney’s synthesis of the phenyl analogue of inthomycin C ((rac)-3).
Scheme 3: Moloney’s synthesis of phenyl analogues of inthomycins A (rac-1) and B (rac-2).
Scheme 4: The first total synthesis of inthomycin B (+)-2 by R. J. K. Taylor.
Scheme 5: R. J. K. Taylor’s total synthesis of racemic inthomycin A (rac)-1.
Scheme 6: The first total synthesis of inthomycin C ((+)-3) by R. J. K. Taylor.
Scheme 7: The first total synthesis of naturally occurring inthomycin C ((–)-3) by Ryu et al.
Scheme 8: Preparation of E,E-iododiene (+)-84 and Z,E- iododiene 85a.
Scheme 9: Hatakeyama’s total synthesis of inthomycin A (+)-1 and inthomycin B (+)-2.
Scheme 10: Hatakeyama’s total synthesis of inthomycin C ((–)-3).
Scheme 11: Maulide’s formal synthesis of racemic inthomycin C ((rac)-3).
Scheme 12: Hale’s synthesis of dienylstannane (+)-69 and enyne (+)-82b intermediates.
Scheme 13: Hale’s total synthesis of inthomycin C ((+)-3).
Scheme 14: Hale and Hatakeyama’s resynthesis of (3R)-inthomycin C (−)-3 Mosher esters.
Scheme 15: Reddy’s formal syntheses of inthomycin C (+)-3 and inthomycin C ((−)-3).
Scheme 16: Synthesis of the cross-metathesis precursors (rac)-118 and 121.
Scheme 17: Donohoe’s total synthesis of inthomycin C ((−)-3).
Scheme 18: Synthesis of dienylboronic ester (E,E)-128.
Scheme 19: Synthesis of the alkenyl iodides (Z)- and (E)-130.
Scheme 20: Burton’s total synthesis of inthomycin B ((+)-2).
Scheme 21: Burton’s total synthesis of inthomycin C ((−)-3).
Scheme 22: Burton’s total synthesis of inthomycin A ((+)-1).
Scheme 23: Synthesis of common intermediate (Z)-(+)-143a.
Scheme 24: Synthesis of (Z)-and (E)-selective fragments (+)-145a–c.
Scheme 25: Kim’s total synthesis of inthomycins A (+)-1 and B (+)-2.
Scheme 26: Completion of total synthesis of inthomycin C ((–)-3) by Kim.
Tuning the stability of alkoxyisopropyl protection groups
- Zehong Liang,
- Henna Koivikko,
- Mikko Oivanen and
- Petri Heinonen
Beilstein J. Org. Chem. 2019, 15, 746–751, doi:10.3762/bjoc.15.70
- and 7.7-fold faster cleaved than the MIP derivative. The more electron-withdrawing trifluoroethoxy group strongly stabilizes the acetal, making it 30-fold more stable compared to MIP protection. Only minor differences are observed between the stabilities of acetal protection on the primary 5’- and on
Graphical Abstract
Figure 1: Reagents for acetal protections.
Scheme 1: Synthesis of 2-alkoxyprop-2-yl-protected thymidines. Reagents and conditions (i) 7 equiv 1a–e, 0.5 ...
Figure 2: Enol ether 8a: R1 = TBS and 8b: R1 = H.
Scheme 2: Proposed acetal hydrolysis pathways.
Synthesis of trifluoromethylated 2H-azirines through Togni reagent-mediated trifluoromethylation followed by PhIO-mediated azirination
- Jiyun Sun,
- Xiaohua Zhen,
- Huaibin Ge,
- Guangtao Zhang,
- Xuechan An and
- Yunfei Du
Beilstein J. Org. Chem. 2018, 14, 1452–1458, doi:10.3762/bjoc.14.123
- , R2 = H) with PhIO in 2,2,2-trifluoroethanol (TFE) afforded 2-trifluoroethoxy-2H-azirines 4 [57]. The latter process involves an intermolecular oxidative trifluoroethoxylation and the subsequent oxidative intramolecular azirination. In continuation of our interest in the construction of the 2H-azirine
Graphical Abstract
Figure 1: Representative pharmaceutical agents bearing the CF3 group.
Figure 2: The structures of the Togni reagents 1-(trifluoromethyl)-1,2-benziodoxol-3(1H)-one (1) and trifluor...
Scheme 1: Our previous hypervalent iodine-mediated synthesis of 2H-azirine compounds.
Scheme 2: Study on the presumed Togni reagent 1-mediated trifluoromethylation followed by PhIO-mediated aziri...
Scheme 3: Togni reagent/PhIO-mediated one-pot synthesis of β-trifluoromethyl 2H-azirines. Reaction conditions...
Scheme 4: Control study with TEMPO.
Scheme 5: Proposed mechanism for the Togni reagent-mediated trifluoromethylation of enamines.
Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines
- Satoru Mori and
- Norio Shibata
Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224
- property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed
- by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives
- . Keywords: aggregation; fluorine; phthalocyanine; subphthalocyanine; trifluoroethoxy; Introduction Phthalocyanines [1][2][3] are analogues of porphyrin condensed with four isoindoline units via a nitrogen atom and exhibit a deep blue color due to their wide 18π electron conjugation. Among them, the most
Graphical Abstract
Scheme 1: Synthesis of trifluoroethoxy-substituted phthalocyanine.
Scheme 2: Synthesis of trifluoroethoxy-substituted binuclear phthalocyanine 5 in Solkane® 365 mfc.
Scheme 3: Synthesis of trifluoroethoxy-substituted unsymmetrical phthalocyanines.
Scheme 4: Synthesis of trifluoroethoxy-substituted phthalocyanine dimers linked at the β-position.
Figure 1: Structure of trifluoroethoxy-substituted phthalocyanine dimers linked at the α-position.
Figure 2: Structure of trifluoroethoxy-substituted dimer via a diacetylene linker.
Figure 3: UV–vis spectra of 9 (A) and 5 (B).
Figure 4: Structure of binuclear phthalocyanines linked by a triazole linker.
Figure 5: Structure of trinuclear phthalocyanines linked by a triazole linker, and windmill-like molecular st...
Scheme 5: Synthesis of trifluoroethoxy-substituted phthalocyanines conjugated with peptides.
Scheme 6: Synthesis of trifluoroethoxy-substituted phthalocyanines conjugated with deoxyribonucleosides.
Scheme 7: Synthesis of trifluoroethoxy-substituted phthalocyanines conjugated with cyclodextrin.
Figure 6: Direction of energy transfer of phthalocyanine–fullerene conjugates.
Scheme 8: Synthesis of fluoropolymer-bearing phthalocyanine side groups.
Scheme 9: Synthesis of trifluoroethoxy-substituted double-decker type phthalocyanines.
Scheme 10: Synthesis of trifluoroethoxy-substituted subphthalocyanine.
Figure 7: Structure of axial ligand substituted subphthalocyanine hybrid dyes.
Scheme 11: Synthesis of subphthalocyanine homodimers.
Scheme 12: Synthesis of subphthalocyanine heterodimers.
Figure 8: Energy transfer between subphthalocyanine units.
Figure 9: Structure of phthalocyanine and subphthalocyanine benzene-fused homodimers.
Scheme 13: Synthesis of a phthalocyanine and subphthalocyanine benzene-fused heterodimer.
Figure 10: X-ray crystallography of Pc-subPc (left) and UV–vis spectra of benzene-fused dimers.
Potent triazine-based dehydrocondensing reagents substituted by an amido group
- Munetaka Kunishima,
- Daiki Kato,
- Nobu Kimura,
- Masanori Kitamura,
- Kohei Yamada and
- Kazuhito Hioki
Beilstein J. Org. Chem. 2016, 12, 1897–1903, doi:10.3762/bjoc.12.179
- substituent in place of the methoxy groups. To date, several triazine derivatives possessing phenoxy [15][16], 2,2,2-trifluoroethoxy [17], or N-ethylamino groups [18] in place of the methoxy groups have been prepared, and the reactivity of these compounds in amide-forming reactions has been examined. The
- reactivity of triazine was found to slightly increase following the introduction of electron-withdrawing phenoxy or 2,2,2-trifluoroethoxy groups and decrease upon the inclusion of an electron-donating N-ethylamino group. This result may indicate that the tuning of the π-electron density within the triazine
Graphical Abstract
Scheme 1: Dehydrocondensing reactions using DMT-MM or DMT-Am, and a catalytic amide-forming reaction.
Figure 1: Structures of amido-substituted chlorotriazines.
Scheme 2: Synthesis of amido-substituted chlorotriazines.
Figure 2: Time courses of the amide-forming reactions.
Figure 3: Time courses of the basic Fischer-type esterification.
Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products
- Mikko Passiniemi and
- Ari M.P. Koskinen
Beilstein J. Org. Chem. 2013, 9, 2641–2659, doi:10.3762/bjoc.9.300
- phosphonate, the steric hindrance caused by the interaction of the trifluoroethoxy group with the aldehyde R’ in TS (syn) is smaller compared with aldehyde 1. This allows some of the aldehyde to react via the trans-oxaphosphetane intermediate. Using these reaction conditions no epimerization was observed
Graphical Abstract
Figure 1: Structures of limonene, carvone and thalidomide.
Figure 2: Structure of Garner’s aldehyde.
Scheme 1: (a) i) Boc2O, 1.0 N NaOH (pH >10), dioxane, +5 °C → rt; ii) MeI, K2CO3, DMF, 0 °C → rt (86% over tw...
Scheme 2: (a) AcCl, MeOH, 0 °C → reflux (99%); (b) i) (Boc)2O, Et3N, THF, 0 °C → rt → 50 °C (89%); ii) Me2C(O...
Scheme 3: (a) LiAlH4, THF, rt (93–96%); (b) (COCl)2, DMSO, iPr2NEt, CH2Cl2, −78 °C → −55 °C (99%).
Scheme 4: The Koskinen procedure for the preparation of Garner’s aldehyde. (a) i) AcCl, MeOH, 0 °C → 50 °C (9...
Scheme 5: Burke’s synthesis of Garner’s aldehyde. BDP - bis(diazaphospholane).
Figure 3: Structures of some iminosugars (7, 9), peptide antibiotics (8) and sphingosine (10) and pachastriss...
Scheme 6: Use of Garner’s aldehyde 1 in multistep synthesis.
Scheme 7: Explanation of the anti- and syn-selectivity in the nucleophilic addition reaction.
Scheme 8: Herold’s method: (a) Lithium 1-pentadecyne, HMPT, THF, −78 °C (71%); (b) Lithium 1-pentadecyne, ZnBr...
Scheme 9: (a) Ethyl lithiumpropiolate, HMPT, THF, −78 °C; (b) (S)- or (R)-MTPA, DCC, DMAP, THF, rt (18, 81%) ...
Scheme 10: Coleman’s selectivity studies and their transition state model for the co-ordinated delivery of the...
Scheme 11: (a) PhMgBr, THF, −78 °C → 0 °C [62] or (a) PhMgBr, Et2O, 0 °C [63].
Scheme 12: (a) cat. RhCl3·3H2O, cat. 26, NaOMe, Ph-B(OH)2, aq DME, 80 °C (24, 71%); (b) cat. RhCl3·3H2O, cat. ...
Scheme 13: Lithiated dithiane (3 equiv), CuI (0.3 equiv), BF3·Et2O (6 equiv), THF, −50 °C, 12 h (70%).
Scheme 14: Addition reaction reported by Lam et al. (a) 1-Hexyne, n-BuLi, THF, −15 °C or −40 °C.
Scheme 15: (a) n-BuLi, HMPT, toluene, −78 °C → rt (85%); (b) n-BuLi, ZnCl2, toluene/Et2O, −78 °C → rt (65%).
Scheme 16: (a) n-BuLi, 34, THF, −40 °C [69]; (b) n-BuLi, 35, THF, −78 °C → rt (80%) [70]; (c) n-BuLi, 35, HMPT, THF, −...
Scheme 17: (a) cat. Rh(acac)(CO)2, 42, THF, 40 °C (74%).
Scheme 18: (a) 1-PropynylMgBr, CuI, THF, Me2S, −78 °C (95%); (b) Ethynyltrimethylsilane, EtMgBr, CuI, THF, Me2...
Scheme 19: (a) cat. 50, toluene, 0 °C (52%); (b) cat. 51, toluene, 0 °C (51%); (c) cat. 52, toluene, 0 °C (50%...
Scheme 20: (a) (iPr)3SiH, cat. Ni(COD)2, dimesityleneimidazolium·HCl, t-BuOK, THF, rt.
Scheme 21: (a) Cp2Zr(H)Cl, cat. AgAsF6, CH2Cl2, rt; (b) Cp2Zr(H)Cl, 1-pentadecyne, cat. ZnBr2 in THF for anti-...
Scheme 22: (a) i) 31, n-BuLi, THF, −78 °C; ii) (S)-1, THF, −78 °C; (b) Red-Al, THF, 0 °C.
Scheme 23: (a) 61, n-BuLi, DMPU, toluene, −78 °C, then (S)-1, toluene, −95 °C (57%); (b) 61, n-BuLi, ZnCl2, to...
Scheme 24: Olefin A as an intermediate in natural product synthesis.
Scheme 25: (a) Ph3(Me)PBr, KH, benzene (66%, rac-64) or (b) AlMe3, Zn, CH2I2, THF (76%) [101]; (c) Ph3(Me)PBr, n-Bu...
Scheme 26: (a) Benzene, rt (82%) [108]; (b) K2CO3, MeOH (85%) [89]; (c) iPrOH, [Ir(COD)Cl]2, PPh3, THF, rt (81%) [114].
Scheme 27: Mechanism of the Still–Gennari modification of the HWE reaction leading to both olefin isomers.
Some aspects of radical chemistry in the assembly of complex molecular architectures
- Béatrice Quiclet-Sire and
- Samir Z. Zard
Beilstein J. Org. Chem. 2013, 9, 557–576, doi:10.3762/bjoc.9.61
- remaining fluorine to introduce different substituents, as shown by the simple formation of trifluoroethoxy derivative 64. The adducts derived from xanthate 61 can be used in yet another way. Gentle aminolysis of the xanthate frees a thiol, which, under more basic conditions, displaces the ortho-fluorine to
Graphical Abstract
Scheme 1: Key radical step in the total synthesis of (–)-dendrobine.
Scheme 2: Radical cascade in the total synthesis of (±)-13-deoxyserratine (ACCN = 1,1'-azobis(cyclohexanecarb...
Scheme 3: Formation of the complete skeleton of (±)-fortucine.
Scheme 4: Model radical sequence for the synthesis of quadrone.
Scheme 5: Radical cascade using the Barton decarboxylation.
Scheme 6: Simplified mechanism for the xanthate addition to alkenes.
Scheme 7: Synthesis of β-lactam derivatives.
Scheme 8: Sequential additions to three different alkenes (PhthN = phthalimido).
Scheme 9: Key cascade in the total synthesis of (±)-matrine (43).
Scheme 10: Synthesis of complex tetralones.
Scheme 11: Synthesis of functionalised azaindoline and indole derivatives.
Scheme 12: Synthesis of thiochromanones.
Scheme 13: Synthesis of complex benzothiepinones. Conditions: 1) CF3COOH; 2) RCHO / AcOH (PMB = p-methoxybenzy...
Scheme 14: Formation and capture of a cyclic nitrone.
Scheme 15: Synthesis of bicyclic cyclobutane motifs.
Scheme 16: Construction of the CD rings of steroids.
Scheme 17: Rapid assembly of polyquinanes.
Scheme 18: Formation of a polycyclic structure via an allene intermediate.
Scheme 19: A polycyclic structure via the alkylative Birch reduction.
Scheme 20: Synthesis of polycyclic pyrimidines and indoline structures.
Scheme 21: Construction of a trans-decalin derivative.
Scheme 22: Multiple uses of a chloroacetonyl xanthate.
Scheme 23: A convergent route to spiroketals.
Scheme 24: A modular approach to 3-arylpiperidines.
Scheme 25: A convergent route to cyclopentanols and to functional allenes.
Scheme 26: Allylation and vinylation of a xanthate and an iodide.
Scheme 27: Vinyl epoxides as allylating agents.
Scheme 28: Radical allylations using allylic alcohol derivatives.
Scheme 29: Synthesis of variously substituted lactams.
Scheme 30: Nickel-mediated synthesis of unsaturated lactams.
Scheme 31: Total synthesis of (±)-3-demethoxy-erythratidinone.
Scheme 32: Generation and capture of an iminyl radical from an oxime ester.
Synthesis, reactivity and biological activity of 5-alkoxymethyluracil analogues
- Lucie Brulikova and
- Jan Hlavac
Beilstein J. Org. Chem. 2011, 7, 678–698, doi:10.3762/bjoc.7.80
- , 2,2,2-trifluoroethanol or 2,2,2-trichloroethanol to give the 5-(1-ethoxy-2-iodoethyl) 56, 5-[1-(2-fluoroethoxy)-2-iodoethyl] 57, 5-[1-(2,2,2-trifluoroethoxy)-2-iodoethyl] 58 and 5-[1-(2,2,2-trichloroethoxy)-2-iodoethyl] 59 uracil analogues. Rai and co-workers also used the same procedure to prepare a
Graphical Abstract
Figure 1: Investigated derivatives.
Figure 2: Modifications of uracil ring.
Figure 3: 5-(3,3,3-Trifluoro-1-methoxypropyl)-2'-deoxyuridine (1).
Scheme 1: Synthesis of 5-(3,3,3-trifluoro-1-methoxypropyl)-2'-deoxyuridine (1) and 5-(3,3,3-trifluoro-1-(2-pr...
Scheme 2: Synthesis of 5-(3,3,3-trifluoro-1-methoxyprop-1-yl)-5,6-dihydro-2'-deoxyuridine (8).
Scheme 3: Synthesis of 5-(methoxy-2-haloethyl)-2'-deoxyuridines 12 and 13.
Scheme 4: Synthesis of 5-(1-methoxy-2-iodoethyl) nucleosides 28–30.
Figure 4: [125I] radiolabelled 5-(1-methoxy-2-iodoethyl)-2'-deoxyuridine 31.
Scheme 5: Synthesis of 5-(1-alkoxy-2-iodoethyl) 34–36 and 5-(1-ethoxy-2,2-diiodoethyl)-2'-deoxyuridine (33).
Scheme 6: Synthesis of 5-(1-methoxy-2-iodoethyl)-3',5'-di-O-acetyl-2'-deoxyuridine (38) and 5-(1-ethoxy-2-iod...
Figure 5: 5-(1-Hydroxy(or ethoxy)-2-haloethyl)-3',5'-di-O-acetyl-2'-deoxyuridines 43–46.
Scheme 7: 5-(1-Methoxy-2,2-dihaloethyl)-2'-deoxyuridines 47–49.
Scheme 8: Synthesis of 5-[1-(2-haloethyl(or nitro)ethoxy)-2-iodoethyl]-2'-deoxyuridines 50–54.
Scheme 9: Synthesis of alkoxyuracil analogues 56–61.
Figure 6: 5-(Methoxy-2-haloethyl)uracils 62–64.
Scheme 10: Synthesis of perfluoro derivatives 70–74.
Scheme 11: Synthesis of 1-β-D-arabinofuranosyl-5-(1-methoxy-2-iodoethyl)uracil (79).
Scheme 12: Synthesis of 1-β-D-arabinofuranosyl-5-(2,2-dibromo-1-methoxyethyl)uracil 82 and uridine analogue 83....
Scheme 13: Synthesis of methoxy derivative 87.
Scheme 14: Synthesis of 5-(1-methoxy-2-azidoethyl)-2'-deoxyuridine (93).
Scheme 15: Synthesis of methoxyalkyl derivatives 96 and 97.
Scheme 16: Synthesis of 5-(1-methoxyethyl)-2'-deoxyuridine (100).
Scheme 17: Synthesis of 2'-deoxy-5-(1-methoxyethyl)-4'-thiouridine (104).
Figure 7: 5-(1-Butoxyethyl)uracil 105 and 5-(1-butoxyethyl)-2'-deoxyuridine (106).
Scheme 18: Synthesis of β- and α-anomer of 5-(1-ethoxy-2-methylprop-1-yl)-2'-deoxyuridine.
Scheme 19: Synthesis of 5-(1-acyloxyethyl)-1-(tetrahydrofuran-2-yl)uracils 117 and 118.
Scheme 20: Synthesis of 5-(1,2-diacetoxyethyl)-3',5'-di-O-acetyl-2'-deoxyuridine 120.
Scheme 21: Synthesis of 5-[alkoxy-(4-nitrophenyl)methyl]uracils 124.
Scheme 22: Synthesis of 5-[alkoxy-(4-nitrophenyl)methyl]uridines 126 and 127.
Scheme 23: Synthesis of phosphoramidite 134. Reaction conditions 1: (a) TBDMSCl, imidazole, pyridine, 33 h, 99...
Scheme 24: Synthesis of phosphoramidite 145. (a) B(OCH3)3, CH(OCH3)3, Na2CO3, MeOH, 150 °C; (b) I2, (0.6 equiv...
Figure 8: Oligonucleotide 146.
Scheme 25: Synthesis of phosphoramidite 150.
Figure 9: 2'-Deoxyuridine derivatives 151–154.
Scheme 26: Synthesis of 2'-deoxyuridine derivatives 151–152.
Scheme 27: Synthesis of 5-[3-(2'-deoxyuridin-5-yl)-1-methoxyprop-1-yl]-2'-deoxyuridine (163).
Scheme 28: Synthesis of “metallocenonucleosides” 164 and 167.
Scheme 29: Synthesis of 5-(2,4:3,5-di-O-benzylidene-D-pentahydroxypentyl)-2,4-di-tert-butoxy-pyrimidine 172 an...
Figure 10: α- and β-pseudouridine (174 and 175).
Figure 11: 5'-Modified pseudouridine 176 and secopseudouridines 177, 178.
Figure 12: Methoxy derivatives 12, 13 and 28.
Figure 13: 5-(1-Methoxy-2,2-dihaloethyl)-2'-deoxyuridines 47–49.
Figure 14: 5-(1-Methoxyethyl)-2'-deoxyuridine 100.
Figure 15: 2'-Deoxy-5-(1-methoxyethyl)-4'-thiouridine (104).
Figure 16: 5-(1-Methoxy-2-azidoethyl)-2'-deoxyuridine (93).
Figure 17: 5-[1-(2-Halo(or nitro)ethoxy-2-iodoethyl)]-2'-deoxyuridines 50–54.
Figure 18: 5-[Alkoxy-(4-nitrophenyl)-methyl] uracil analogues 124, 126 and 127.
Figure 19: Methoxyiodoethyl pyrimidine nucleoside 79.
Figure 20: 5-[alkoxy-(4-nitro-phenyl)-methyl]uridines 126 and 127.
