Search for "highly regioselective" in Full Text gives 67 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2019, 15, 801–810, doi:10.3762/bjoc.15.77
Graphical Abstract
Figure 1: Adefovir (1) and its prodrug 2.
Scheme 1: Literature syntheses of 1.
Figure 2: Retrosynthetic analysis of 6 to synthons 9 and 10.
Scheme 2: Forward synthesis of 6 from 9 and 10.
Figure 3: Retrosynthesis of 6 to synthons 14 and 3.
Scheme 3: Application of related alkyl iodide 15 [52].
Scheme 4: Synthesis of 6 and 20 via iodide 14.
Scheme 5: Synthesis of phosphonate 6 using novel salt 21.
Scheme 6: Application of iodide 14 in the synthesis of adefovir analogues.
Figure 4: HMBC spectrum confirms N7-selectivity for the major product 29.
Scheme 7: Attempted synthesis of adefovir dipivoxil (2) exploiting phosphonate 33.
Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28
Graphical Abstract
Figure 1: Cubic octasilsesquioxane.
Scheme 1: Reactivity of vinylsilanes in the presence of ruthenium alkylidene complexes; a) cross metathesis, ...
Figure 2: The scope and limitations of metathesis in transformations of vinyl-substituted siloxanes and silse...
Scheme 2: Application of olefin metathesis in the synthesis and modification of POSS-based materials: a) func...
Figure 3: Olefin metathesis catalysts used in transformations of silsesquioxanes.
Figure 4: Octavinyl-substituted cubic silsesquioxane (OVS) and spherosilicate.
Scheme 3: Cross metathesis of OVS with terminal olefins (stereoselectivity as discussed in the text).
Scheme 4: Cross metathesis of OVS with substituted styrenes.
Scheme 5: Modification of OVS via CM with styrenes.
Figure 5: Vinylbiphenyl chromophore-decorated cubic silsesquioxanes.
Scheme 6: Cross metathesis of OVS with carboranylstyrene.
Scheme 7: Synthesis of octakis[2-(p-carboxyphenyl)ethyl]silsesquioxane via CM and subsequent hydrogenation.
Scheme 8: Cross metathesis of monovinyl-POSS with olefins.
Scheme 9: Cross metathesis of monovinyl-POSS with highly π-conjugated substituted styrenes.
Scheme 10: Cross metathesis of monovinylgermasilsesquioxane with styrenes.
Scheme 11: Cross metathesis of DDSQ-2SiVi with olefins.
Scheme 12: Cross metathesis of DDSQ-2SiVi with substituted styrenes.
Scheme 13: Cross metathesis of (DDSQ-2GeVi) with olefins.
Scheme 14: CM of divinyl-substituted T10 and T12 with 4-bromostyrene (selected isomers are shown).
Scheme 15: Synthesis of vinylstilbene derivatives of T10 and T12 via a sequence of CM and Heck coupling.
Scheme 16: Cross metathesis of allyl-POSS with tert-butyl acrylate and (Z)-1,4-diacetoxy-but-2-ene.
Scheme 17: Cross metathesis of allyl-POSS with olefins.
Scheme 18: Acyclic diene metathesis copolymerization of DDSQ-2SiVi with diolefins.
Scheme 19: Acyclic diene metathesis copolymerization of DDSQ-2GeVi with diolefins.
Scheme 20: Ring-opening metathesis copolymerization of norbornenylethyl-POSS with norbornene.
Scheme 21: Synthesis of a polyethylene–POSS copolymer via ring-opening metathesis copolymerization of norborne...
Scheme 22: ROMP of norbornenylethyl-POSS with 1,5-cyclooctadiene.
Scheme 23: Copolymerization of POSS-functionalized norbornene with DCPD.
Scheme 24: Copolymerization of tris(norbornenylethyl)-POSS with DCPD.
Scheme 25: Copolymerization of N-(propyl-POSS)-7-oxanorbornene-5,6-dicarboximide with 3-(trifluoromethyl)pheny...
Figure 6: Homopolymers and copolymers having POSS groups attached to the main chain via flexible spacers of d...
Scheme 26: Ring-opening metathesis copolymerization of POSS-NBE with methyltetracyclododecene.
Scheme 27: Synthesis of block copolymer via ROMP by sequential monomer addition.
Scheme 28: Synthesis of a liquid crystalline polymer with POSS core in the side chain.
Scheme 29: Sequential synthesis of copolymers of polynorbornene containing POSS and PEO pendant groups.
Scheme 30: Synthesis of rodlike POSS−bottlebrush block copolymers [54].
Scheme 31: Surface-initiated ROMP producing copolymer layers on the surface of CdSe/ZnS quantum dots.
Beilstein J. Org. Chem. 2018, 14, 2829–2837, doi:10.3762/bjoc.14.261
Graphical Abstract
Figure 1: Schematic representation of native α-CD (1) and top view of its primary rim with alphabetic clockwi...
Scheme 1: Synthesis of 6A,6X-diazido-α-CD derivatives 4 via 6A,6X-capped α-CDs 2 and 3 and their regioisomeri...
Scheme 2: Synthesis of 6A,6X- and 6A,6D-diazido-α-CDs via 6A,6X-dibromo-α-CD 5, 6A,6D-dibromo-α-CD 5d interme...
Scheme 3: Synthesis of 6A,6X-diazido-α-CDs via 6A,6X-ditosyl-α-CD intermediates 6 and their regioisomeric rat...
Figure 2: HPLC chromatograms of 6A,6X-diazido-α-CDs 4 of the reactions 1–5, with ACN/water gradient elution a...
Scheme 4: Synthesis of 6A-azido-6X-mesitylenesulfonyl-α-CD 8 and conversion into 6A,6X-diazido-α-CD 4.
Figure 3: HPLC chromatograms of reaction 7 with separated 6A-azido-α-CD 7 as starting material and regioisome...
Figure 4: HPLC chromatograms of 6A-azido-6X-mesitylenesulfonyl-α-CD 8 (reaction 6): a) analytical and b) prep...
Figure 5: 1H NMR spectrum of the AC regioisomer 8c as a mixture of pseudoenantiomers prepared through reactio...
Figure 6: 13C NMR spectrum of the AC regioisomer 8c as a mixture of pseudoenantiomers prepared through reacti...
Figure 7: HPLC–MS chromatogram with the separated pseudoenantiomers of 6A-azido-6B-mesitylenesulfonyl-α-CD 8b...
Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202
Graphical Abstract
Scheme 1: Cobalt-catalyzed C–H carbonylation.
Scheme 2: Hydroarylation by C–H activation.
Scheme 3: Pathways for cobalt-catalyzed hydroarylations.
Scheme 4: Co-catalyzed hydroarylation of alkynes with azobenzenes.
Scheme 5: Co-catalyzed hydroarylation of alkynes with 2-arylpyridines.
Scheme 6: Co-catalyzed addition of azoles to alkynes.
Scheme 7: Co-catalyzed addition of indoles to alkynes.
Scheme 8: Co-catalyzed hydroarylation of alkynes with imines.
Scheme 9: A plausible pathway for Co-catalyzed hydroarylation of alkynes.
Scheme 10: Co-catalyzed anti-selective C–H addition to alkynes.
Scheme 11: Co(III)-catalyzed hydroarylation of alkynes with indoles.
Scheme 12: Co(III)-catalyzed branch-selective hydroarylation of alkynes.
Scheme 13: Co(III)-catalyzed hydroarylation of terminal alkynes with arenes.
Scheme 14: Co(III)-catalyzed hydroarylation of alkynes with amides.
Scheme 15: Co(III)-catalyzed C–H alkenylation of arenes.
Scheme 16: Co-catalyzed alkylation of substituted benzamides with alkenes.
Scheme 17: Co-catalyzed switchable hydroarylation of styrenes with 2-aryl pyridines.
Scheme 18: Co-catalyzed linear-selective hydroarylation of alkenes with imines.
Scheme 19: Co-catalyzed linearly-selective hydroarylation of alkenes with N–H imines.
Scheme 20: Co-catalyzed branched-selective hydroarylation of alkenes with imines.
Scheme 21: Mechanism of Co-catalyzed hydroarylation of alkenes.
Scheme 22: Co-catalyzed intramolecular hydroarylation of indoles.
Scheme 23: Co-catalyzed asymmetric hydroarylation of alkenes with indoles.
Scheme 24: Co-catalyzed hydroarylation of alkenes with heteroarenes.
Scheme 25: Co(III)-catalyzed hydroarylation of activated alkenes with 2-phenyl pyridines.
Scheme 26: Co(III)-catalyzed C–H alkylation of arenes.
Scheme 27: Co(III)-catalyzed C2-alkylation of indoles.
Scheme 28: Co(III)-catalyzed switchable hydroarylation of alkyl alkenes with indoles.
Scheme 29: Co(III)-catalyzed C2-allylation of indoles.
Scheme 30: Co(III)-catalyzed ortho C–H alkylation of arenes with maleimides.
Scheme 31: Co(III)-catalyzed hydroarylation of maleimides with arenes.
Scheme 32: Co(III)-catalyzed hydroarylation of allenes with arenes.
Scheme 33: Co-catalyzed hydroarylative cyclization of enynes with carbonyl compounds.
Scheme 34: Mechanism for the Co-catalyzed hydroarylative cyclization of enynes with carbonyl compounds.
Scheme 35: Co-catalyzed addition of 2-arylpyridines to aromatic aldimines.
Scheme 36: Co-catalyzed addition of 2-arylpyridines to aziridines.
Scheme 37: Co(III)-catalyzed hydroarylation of imines with arenes.
Scheme 38: Co(III)-catalyzed addition of arenes to ketenimines.
Scheme 39: Co(III)-catalyzed three-component coupling.
Scheme 40: Co(III)-catalyzed hydroarylation of aldehydes.
Scheme 41: Co(III)-catalyzed addition of arenes to isocyanates.
Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143
Graphical Abstract
Figure 1: Some sulfur-containing natural products.
Figure 2: Some natural products incorporating β-hydroxy sulfide moieties.
Figure 3: Some synthetic β-hydroxy sulfides of clinical value.
Scheme 1: Alumina-mediated synthesis of β-hydroxy sulfides, ethers, amines and selenides from epoxides.
Scheme 2: β-Hydroxy sulfide syntheses by ring opening of epoxides under different Lewis and Brønsted acid and...
Scheme 3: n-Bu3P-catalyzed thiolysis of epoxides and aziridines to provide the corresponding β-hydroxy and β-...
Scheme 4: Zinc(II) chloride-mediated thiolysis of epoxides.
Scheme 5: Thiolysis of epoxides and one-pot oxidation to β-hydroxy sulfoxides under microwave irradiation.
Scheme 6: Gallium triflate-catalyzed ring opening of epoxides and one-pot oxidation.
Scheme 7: Thiolysis of epoxides and one-pot oxidation to β-hydroxy sulfoxides using Ga(OTf)3 as a catalyst.
Scheme 8: Ring opening of epoxide using ionic liquids under solvent-free conditions.
Scheme 9: N-Bromosuccinimide-catalyzed ring opening of epoxides.
Scheme 10: LiNTf2-mediated epoxide opening by thiophenol.
Scheme 11: Asymmetric ring-opening of cyclohexene oxide with various thiols catalyzed by zinc L-tartrate.
Scheme 12: Catalytic asymmetric ring opening of symmetrical epoxides with t-BuSH catalyzed by (R)-GaLB (43) wi...
Scheme 13: Asymmetric ring opening of meso-epoxides by p-xylenedithiol catalyzed by a (S,S)-(salen)Cr complex.
Scheme 14: Desymmetrization of meso-epoxide with thiophenol derivatives.
Scheme 15: Enantioselective ring-opening reaction of meso-epoxides with ArSH catalyzed by a C2-symmetric chira...
Scheme 16: Enantioselective ring-opening reaction of stilbene oxides with ArSH catalyzed by a C2-symmetric chi...
Scheme 17: Asymmetric desymmetrization of meso-epoxides using BINOL-based Brønsted acid catalysts.
Scheme 18: Lithium-BINOL-phosphate-catalyzed desymmetrization of meso-epoxides with aromatic thiols.
Scheme 19: Ring-opening reactions of cyclohexene oxide with thiols by using CPs 1-Eu and 2-Tb.
Scheme 20: CBS-oxazaborolidine-catalyzed borane reduction of β-keto sulfides.
Scheme 21: Preparation of β-hydroxy sulfides via connectivity.
Scheme 22: Baker’s yeast-catalyzed reduction of sulfenylated β-ketoesters.
Scheme 23: Sodium-mediated ring opening of epoxides.
Scheme 24: Disulfide bond cleavage-epoxide opening assisted by tetrathiomolybdate.
Scheme 25: Proposed reaction mechanism of disulfide bond cleavage-epoxide opening assisted by tetrathiomolybda...
Scheme 26: Cyclodextrin-catalyzed difunctionalization of alkenes.
Scheme 27: Zinc-catalyzed synthesis of β-hydroxy sulfides from disulfides and alkenes.
Scheme 28: tert-Butyl hydroperoxide-catalyzed hydroxysulfurization of alkenes.
Scheme 29: Proposed mechanism of the radical hydroxysulfurization.
Scheme 30: Rongalite-mediated synthesis of β-hydroxy sulfides from styrenes and disulfides.
Scheme 31: Proposed mechanism of Rongalite-mediated synthesis of β-hydroxy sulfides from styrenes and disulfid...
Scheme 32: Copper(II)-catalyzed synthesis of β-hydroxy sulfides 15e,f from alkenes and basic disulfides.
Scheme 33: CuI-catalyzed acetoxysulfenylation of alkenes.
Scheme 34: CuI-catalyzed acetoxysulfenylation reaction mechanism.
Scheme 35: One-pot oxidative 1,2-acetoxysulfenylation of Baylis–Hillman products.
Scheme 36: Proposed mechanism for the oxidative 1,2-acetoxysulfination of Baylis–Hillman products.
Scheme 37: 1,2-Acetoxysulfenylation of alkenes using DIB/KI.
Scheme 38: Proposed reaction mechanism of the diacetoxyiodobenzene (DIB) and KI-mediated 1,2-acetoxysulfenylat...
Scheme 39: Catalytic asymmetric thiofunctionalization of unactivated alkenes.
Scheme 40: Proposed catalytic cycle for asymmetric sulfenofunctionalization.
Scheme 41: Synthesis of thiosugars using intramolecular thiol-ene reaction.
Scheme 42: Synthesis of leukotriene C-1 by Corey et al.: (a) N-(trifluoroacetyl)glutathione dimethyl ester (3 ...
Scheme 43: Synthesis of pteriatoxins with epoxide thiolysis to attain β-hydroxy sulfides. Reagents: (a) (1) K2...
Scheme 44: Synthesis of peptides containing a β-hydroxy sulfide moiety.
Scheme 45: Synthesis of diltiazem (12) using biocatalytic resolution of an epoxide followed by thiolysis.
Beilstein J. Org. Chem. 2018, 14, 1192–1202, doi:10.3762/bjoc.14.100
Graphical Abstract
Scheme 1: Generation and reaction of cationic species generated by “indirect cation pool” methods.
Figure 1: (a) 1H NMR of N-acyliminium ion C1 in CD2Cl2 at −80 °C (600 MHz). (b) Preferred conformation of C1.
Figure 2: (a) 1H NMR spectrum of C3 in CD2Cl2 at −60 °C (400 MHz). (b) Preferred conformation of C3.
Figure 3: (a) 1H NMR spectrum of C5 in CD2Cl2 at −60 °C (400 MHz). (b) Preferred conformation of C5.
Figure 4: Summary of the conformations of N-acyliminium ions C1–C6.
Figure 5: Stevens’ hypothesis on the tendency of the addition of nucleophiles to N-acyliminium ions. The subs...
Figure 6: A plausible mechanism of the observed diastereoselective reaction of the N-acyliminium ions.
Figure 7: Comparison of ΔG for the pseudo-equatorial and pseudo-axial conformations of C1–C6 at the B3LYP/6-3...
Beilstein J. Org. Chem. 2018, 14, 796–802, doi:10.3762/bjoc.14.67
Graphical Abstract
Scheme 1: Reactions of substituted allenes with HVI reagents.
Scheme 2: Chlorination of p-tolylallene (2a) with (dichloroiodo)benzene (1a).
Scheme 3: Chlorination of various aryl-substituted allenes. General conditions: Allene 2a (0.2 mmol, 1 equiv)...
Scheme 4: Chlorination of various α-substituted phenylallene derivatives. General conditions: Allene 2a (0.2 ...
Scheme 5: Chlorination of methoxy-substituted α-methyl phenylallenes. General conditions: Allene 2a (0.2 mmol...
Scheme 6: Control reactions: (a) chlorination of deuterated biphenylallene [D2]-2b; (b) reaction with TEMPO.
Figure 1: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272
Graphical Abstract
Scheme 1: Trifluoromethylation of enol acetates by Langlois.
Scheme 2: Trifluoromethylation of (het)aryl enol acetates.
Scheme 3: Mechanism for the trifluoromethylation of enol acetates.
Scheme 4: Oxidative trifluoromethylation of unactivated olefins and mechanistic pathway.
Scheme 5: Oxidative trifluoromethylation of acetylenic substrates.
Scheme 6: Metal free trifluoromethylation of styrenes.
Scheme 7: Synthesis of α-trifluoromethylated ketones by oxytrifluoromethylation of heteroatom-functionalised ...
Scheme 8: Catalysed photoredox trifluoromethylation of vinyl azides.
Scheme 9: Oxidative difunctionalisation of alkenyl MIDA boronates.
Scheme 10: Synthesis of β-trifluoromethyl ketones from cyclopropanols.
Scheme 11: Aryltrifluoromethylation of allylic alcohols.
Scheme 12: Cascade multicomponent synthesis of nitrogen heterocycles via azotrifluoromethylation of alkenes.
Scheme 13: Photocatalytic azotrifluoromethylation of alkenes with aryldiazonium salts and CF3SO2Na.
Scheme 14: Copper-promoted intramolecular aminotrifluoromethylation of alkenes with CF3SO2Na.
Scheme 15: Oxytrifluoromethylation of alkenes with CF3SO2Na and hydroxamic acid.
Scheme 16: Manganese-catalysed oxytrifluoromethylation of styrene derivatives.
Scheme 17: Oxytrifluoromethylation of alkenes with NMP/O2 and CF3SO2Na.
Scheme 18: Intramolecular oxytrifluoromethylation of alkenes.
Scheme 19: Hydrotrifluoromethylation of styrenyl alkenes and unactivated aliphatic alkenes.
Scheme 20: Hydrotrifluoromethylation of electron-deficient alkenes.
Scheme 21: Hydrotrifluoromethylation of alkenes by iridium photoredox catalysis.
Scheme 22: Iodo- and bromotrifluoromethylation of alkenes by CF3SO2Na/I2O5 or CF3SO2Na / NaBrO3.
Scheme 23: N-methyl-9-mesityl acridinium and visible-light-induced chloro-, bromo- and SCF3 trifluoromethylati...
Scheme 24: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na / TBHP by Lipshutz.
Scheme 25: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/TBHP reported by Lei.
Scheme 26: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/(NH4)2S2O8.
Scheme 27: Metal-free carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/K2S2O8 reported by Wang.
Scheme 28: Metal-free carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/PIDA reported by Fu.
Scheme 29: Metal-free cascade trifluoromethylation/cyclisation of N-arylmethacrylamides (a) and enynes (b) wit...
Scheme 30: Trifluoromethylation/cyclisation of N-arylcinnamamides: Synthesis of 3,4-disubstituted dihydroquino...
Scheme 31: Trifluoromethylation/cyclisation of aromatic-containing unsaturated ketones.
Scheme 32: Chemo- and regioselective cascade trifluoromethylation/heteroaryl ipso-migration of unactivated alk...
Scheme 33: Copper-mediated 1,2-bis(trifluoromethylation) of alkenes.
Scheme 34: Trifluoromethylation of aromatics with CF3SO2Na reported by Langlois.
Scheme 35: Baran’s oxidative C–H trifluoromethylation of heterocycles.
Scheme 36: Trifluoromethylation of acetanilides and anilines.
Scheme 37: Trifluoromethylation of heterocycles in water.
Scheme 38: Trifluoromethylation of coumarins in a continuous-flow reactor.
Scheme 39: Oxidative trifluoromethylation of coumarins, quinolines and pyrimidinones.
Scheme 40: Oxidative trifluoromethylation of pyrimidinones and pyridinones.
Scheme 41: Phosphovanadomolybdic acid-catalysed direct C−H trifluoromethylation.
Scheme 42: Oxidative trifluoromethylation of imidazopyridines and imidazoheterocycles.
Scheme 43: Oxidative trifluoromethylation of imidazoheterocycles and imidazoles in ionic liquid/water.
Scheme 44: Oxidative trifluoromethylation of 8-aminoquinolines.
Scheme 45: Oxidative trifluoromethylation of various 8-aminoquinolines using the supported catalyst CS@Cu(OAc)2...
Scheme 46: Oxidative trifluoromethylation of the naphthylamide 70.
Scheme 47: Oxidative trifluoromethylation of various arenes in the presence of CF3SO2Na and sodium persulfate.
Scheme 48: Trifluoromethylation of electron-rich arenes and unsymmetrical biaryls with CF3SO2Na in the presenc...
Figure 1: Trifluoromethylated coumarin and flavone.
Scheme 49: Metal-free trifluoromethylation catalysed by a photoredox organocatalyst.
Scheme 50: Quinone-mediated trifluoromethylation of arenes and heteroarenes.
Scheme 51: Metal- and oxidant-free photochemical trifluoromethylation of arenes.
Scheme 52: Copper-mediated trifluoromethylation of arenediazonium tetrafluoroborates.
Scheme 53: Oxidative trifluoromethylation of aryl- and heteroarylboronic acids.
Scheme 54: Oxidative trifluoromethylation of aryl- and vinylboronic acids.
Scheme 55: Oxidative trifluoromethylation of unsaturated potassium organotrifluoroborates.
Scheme 56: Oxidative trifluoromethylation of (hetero)aryl- and vinyltrifluoroborates.
Scheme 57: Copper−catalysed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 58: Iron-mediated decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 59: Cu/Ag-catalysed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 60: I2O5-Promoted decarboxylative trifluoromethylation of cinnamic acids.
Scheme 61: Silver(I)-catalysed denitrative trifluoromethylation of β-nitrostyrenes.
Scheme 62: Copper-catalysed direct trifluoromethylation of styrene derivatives.
Scheme 63: Transition-metal-free synthesis of β-trifluoromethylated enamines.
Scheme 64: I2O5-mediated iodotrifluoromethylation of alkynes.
Scheme 65: Silver-catalysed tandem trifluoromethylation/cyclisation of aryl isonitriles.
Scheme 66: Photoredox trifluoromethylation of 2-isocyanobiphenyls.
Scheme 67: Trifluoromethylation of potassium alkynyltrifluoroborates with CF3SO2Na.
Scheme 68: N-trifluoromethylation of nitrosoarenes with CF3SO2Na (SQ: semiquinone).
Scheme 69: Trifluoromethylation of disulfides with CF3SO2Na.
Scheme 70: Trifluoromethylation of thiols with CF3SO2Na/I2O5.
Scheme 71: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/(EtO)2P(O)H/CuCl/DMSO.
Scheme 72: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/(EtO)2P(O)H/TMSCl.
Scheme 73: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PPh3/N-chlorophthalimide.
Scheme 74: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PCl3.
Scheme 75: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PCl3.
Scheme 76: Trifluoromethylsulfenylation of aryl iodides with in situ generated CuSCF3 (DMI: 1,3-dimethyl-2-imi...
Scheme 77: Pioneering trifluoromethylsulfinylation of N, O, and C-nucleophiles.
Scheme 78: Trifluoromethylsulfinylation of (1R,2S)-ephedrine (Im: imidazole; DIEA: N,N-diisopropylethylamine).
Scheme 79: Trifluoromethylsulfinylation of substituted benzenes with CF3SO2Na/CF3SO3H.
Scheme 80: Trifluoromethylsulfinylation of indoles with CF3SO2Na/P(O)Cl3.
Scheme 81: Trifluoromethylsulfinylation of indoles with CF3SO2Na/PCl3.
Scheme 82: Formation of triflones from benzyl bromides (DMA: dimethylacetamide).
Scheme 83: Formation of α-trifluoromethylsulfonyl ketones, esters, and amides.
Scheme 84: Allylic trifluoromethanesulfonylation of aromatic allylic alcohols.
Scheme 85: Copper-catalysed couplings of aryl iodonium salts with CF3SO2Na.
Scheme 86: Palladium-catalysed trifluoromethanesulfonylation of aryl triflates and chlorides with CF3SO2Na.
Scheme 87: Copper-catalysed coupling of arenediazonium tetrafluoroborates with CF3SO2Na.
Scheme 88: Synthesis of phenyltriflone via coupling of benzyne with CF3SO2Na.
Scheme 89: Synthesis of 1-trifluoromethanesulfonylcyclopentenes from 1-alkynyl-λ3-bromanes and CF3SO2Na.
Scheme 90: One-pot synthesis of functionalised vinyl triflones.
Scheme 91: Regioselective synthesis of vinyltriflones from styrenes.
Scheme 92: Trifluoromethanesulfonylation of alkynyl(phenyl) iodonium tosylates by CF3SO2Na.
Scheme 93: Synthesis of thio- and selenotrifluoromethanesulfonates.
Beilstein J. Org. Chem. 2017, 13, 2617–2625, doi:10.3762/bjoc.13.259
Graphical Abstract
Figure 1: Summary of the present study.
Scheme 1: Hydrogenation of compounds 4–6 and preparation of N1(3)-unsubstituted compounds 9–11d.
Figure 2: Molecular structure of compound 11b. Two enantiomers form a heterochiral dimer in the crystal state...
Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248
Graphical Abstract
Scheme 1: Preparation of 2I-O-, 3I-O- and 6I-O-naphthylallyl derivatives of γ-CD by cross-metathesis.
Scheme 2: Preparation of 2-O-, 3-O- and 6-O-NA derivatives of γ-CD by direct alkylation (see Table 1 for the yields ...
Figure 1: Volume-weighted distribution functions for water solutions of 2-O- (2a), 3-O- (2b), and 6-O- (2c) N...
Figure 2: Distribution functions for 2-O- (2a), 3-O- (2b), and 6-O- (2c) NA-γ-CD regioisomers in 50% MeOH (v/...
Figure 3: Volume-weighted distribution functions for the 3-O- (2b) and 6-O- (2c) NA-γ-CD regioisomer at diffe...
Figure 4: Effect of increasing concentration and sonication on the morphology of the 3-O-derivative 2b. A to ...
Figure 5: Effect of increasing concentration and sonication on the morphology of the 2-O-derivative 2a. A: 2 ...
Figure 6: Effect of increasing concentration and sonication on the morphology of the 6-O-derivative 2c. A: 0....
Figure 7: Heat change for injection per mole of NA-γ-CD added as a function of the total concentration of NA-...
Figure 8: 1H NMR spectra of 2-O-derivative 2a in D2O at concentrations of 100, 10, and 1 mM.
Figure 9: 1H NMR spectra of 3-O-derivative 2b in D2O at concentrations of 100, 10, and 1 mM.
Figure 10: Putative objects and interactions in naphthylallyl-γ-CD solution, depicted schematically for 6I-O-n...
Beilstein J. Org. Chem. 2017, 13, 2396–2407, doi:10.3762/bjoc.13.237
Graphical Abstract
Figure 1: Hydrogen coupling constants (3JH-H) of (a) H6–H7 for 3a and (b) H5–H6 for 5h.
Figure 2: LUMO coefficients for (a) β-enaminones 1a,h, and their (b) conjugated acids.
Figure 3:
(a) 1H and (b) 13C NMR spectra demonstrating the 3d4d equilibrium in DMSO-d6 at 25 °C.
Figure 4: ORTEP® [45] plot of 7a with thermal ellipsoids drawn at 50% probability level.
Figure 5: Tetrazolo[1,5-a]pyrimidine observed in solution (CDCl3 and DMSO-d6) and 2-azidopyrimidine observed ...
Figure 6: ORTEP® [45] plot of 8i with thermal ellipsoids drawn at 50% probability level.
Figure 7: Representation of the possible equilibrium existing between 6i, 7i, and 8i.
Beilstein J. Org. Chem. 2017, 13, 2023–2027, doi:10.3762/bjoc.13.200
Graphical Abstract
Scheme 1: Synthesis of 1-(tert-butylperoxy)-2-iodoethanes.
Scheme 2: Direct vicinal difunctionalization of alkenes. All reactions were carried out on a 2.0 mmol scale u...
Scheme 3: Possible reaction mechanism.
Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186
Graphical Abstract
Scheme 1: Mechanochemical aldol condensation reactions [48].
Scheme 2: Enantioselective organocatalyzed aldol reactions under mechanomilling. a) Based on binam-(S)-prolin...
Scheme 3: Mechanochemical Michael reaction [51].
Scheme 4: Mechanochemical organocatalytic asymmetric Michael reaction [52].
Scheme 5: Mechanochemical Morita–Baylis–Hillman (MBH) reaction [53].
Scheme 6: Mechanochemical Wittig reactions [55].
Scheme 7: Mechanochemical Suzuki reaction [56].
Scheme 8: Mechanochemical Suzuki–Miyaura coupling by LAG [57].
Scheme 9: Mechanochemical Heck reaction [59].
Scheme 10: a) Sonogashira coupling under milling conditions. b) The representative example of a double Sonogas...
Scheme 11: Copper-catalyzed CDC reaction under mechanomilling [67].
Scheme 12: Asymmetric alkynylation of prochiral sp3 C–H bonds via CDC [68].
Scheme 13: Fe(III)-catalyzed CDC coupling of 3-benzylindoles [69].
Scheme 14: Mechanochemical synthesis of 3-vinylindoles and β,β-diindolylpropionates [70].
Scheme 15: Mechanochemical C–N bond construction using anilines and arylboronic acids [78].
Scheme 16: Mechanochemical amidation reaction from aromatic aldehydes and N-chloramine [79].
Scheme 17: Mechanochemical CDC between benzaldehydes and benzyl amines [81].
Scheme 18: Mechanochemical protection of -NH2 and -COOH group of amino acids [85].
Scheme 19: Mechanochemical Ritter reaction [87].
Scheme 20: Mechanochemical synthesis of dialkyl carbonates [90].
Scheme 21: Mechanochemical transesterification reaction using basic Al2O3 [91].
Scheme 22: Mechanochemical carbamate synthesis [92].
Scheme 23: Mechanochemical bromination reaction using NaBr and oxone [96].
Scheme 24: Mechanochemical aryl halogenation reactions using NaX and oxone [97].
Scheme 25: Mechanochemical halogenation reaction of electron-rich arenes [88,98].
Scheme 26: Mechanochemical aryl halogenation reaction using trihaloisocyanuric acids [100].
Scheme 27: Mechanochemical fluorination reaction by LAG method [102].
Scheme 28: Mechanochemical Ugi reaction [116].
Scheme 29: Mechanochemical Passerine reaction [116].
Scheme 30: Mechanochemical synthesis of α-aminonitriles [120].
Scheme 31: Mechanochemical Hantzsch pyrrole synthesis [121].
Scheme 32: Mechanochemical Biginelli reaction by subcomponent synthesis approach [133].
Scheme 33: Mechanochemical asymmetric multicomponent reaction[134].
Scheme 34: Mechanochemical Paal–Knorr pyrrole synthesis [142].
Scheme 35: Mechanochemical synthesis of benzothiazole using ZnO nano particles [146].
Scheme 36: Mechanochemical synthesis of 1,2-di-substituted benzimidazoles [149].
Scheme 37: Mechanochemical click reaction using an alumina-supported Cu-catalyst [152].
Scheme 38: Mechanochemical click reaction using copper vial [155].
Scheme 39: Mechanochemical indole synthesis [157].
Scheme 40: Mechanochemical synthesis of chromene [158].
Scheme 41: Mechanochemical synthesis of azacenes [169].
Scheme 42: Mechanochemical oxidative C-P bond formation [170].
Scheme 43: Mechanochemical C–chalcogen bond formation [171].
Scheme 44: Solvent-free synthesis of an organometallic complex.
Scheme 45: Selective examples of mechano-synthesis of organometallic complexes. a) Halogenation reaction of Re...
Scheme 46: Mechanochemical activation of C–H bond of unsymmetrical azobenzene [178].
Scheme 47: Mechanochemical synthesis of organometallic pincer complex [179].
Scheme 48: Mechanochemical synthesis of tris(allyl)aluminum complex [180].
Scheme 49: Mechanochemical Ru-catalyzed olefin metathesis reaction [181].
Scheme 50: Rhodium(III)-catalyzed C–H bond functionalization under mechanochemical conditions [182].
Scheme 51: Mechanochemical Csp2–H bond amidation using Ir(III) catalyst [183].
Scheme 52: Mechanochemical Rh-catalyzed Csp2–X bond formation [184].
Scheme 53: Mechanochemical Pd-catalyzed C–H activation [185].
Scheme 54: Mechanochemical Csp2–H bond amidation using Rh catalyst.
Scheme 55: Mechanochemical synthesis of indoles using Rh catalyst [187].
Scheme 56: Mizoroki–Heck reaction of aminoacrylates with aryl halide in a ball-mill [58].
Scheme 57: IBX under mechanomilling conditions [8].
Scheme 58: Thiocarbamoylation of anilines; trapping of reactive aryl-N-thiocarbamoylbenzotriazole intermediate...
Beilstein J. Org. Chem. 2017, 13, 1350–1360, doi:10.3762/bjoc.13.132
Graphical Abstract
Scheme 1: The structures of quinoxalin-2(1H)-ones 1, 2 and 3,4-dihydroquinoxalin-2(1H)-ones 3. An acylmethyl ...
Figure 1: The structures including some of their physical and biological properties of 3,4-dihydroqunoxalin-2...
Scheme 2: Selective synthesis of both 3,4-dihydroquinoxalin-2(1H)-one regioisomers 16e (SYN) and 17e (ANTI).
Scheme 3: The proposed mechanism for the synthesis of 3-methylquinoxalin-2(1H)-one regioisomers 22 and 23. In...
Scheme 4: The regioselective syntheses of both quinoxalin-2(1H)-ones 27 (ANTI) and 26 (SYN).
Scheme 5: The selective synthesis of substituted quinoxalin-2(1H)-ones 31 from 28 via three reaction steps.
Scheme 6: Regioselectivity switching based on carbonyl activation of 4-chlorobenzoylpyruvates 12a,b by p-TsOH...
Figure 2: The interactions and assignments, obtained after analyses of NMR spectra, allowed us to distinguish...
Figure 3: NMR assignments for compound 16d.
Figure 4: NMR assignments for compound 17d.
Beilstein J. Org. Chem. 2017, 13, 257–266, doi:10.3762/bjoc.13.29
Graphical Abstract
Scheme 1: Mechanism proposed for the formation of compound 5.
Scheme 2: Mechanism proposed for the formation of compound 9a.
Figure 1: ORTEP plot of 6, 9c, and 12g with the thermal ellipsoids drawn at the following probability levels:...
Beilstein J. Org. Chem. 2016, 12, 2906–2915, doi:10.3762/bjoc.12.290
Graphical Abstract
Scheme 1: Synthesis of allylphosphonates from acyclic MBH adducts.
Scheme 2: Synthesis of γ-ketoallylphosphonates from cyclic MBH adducts.
Scheme 3: Proposed mechanism for DMAP-mediated direct nucleophilic α-substitution of MBH alcohol 1a.
Scheme 4: Direct conversion of acyclic MBH alcohols 3a–c into γ-ketoallylphosphonates 4a–f.
Scheme 5: I2-Catalyzed direct synthesis of γ-tosylaminophosphonates 6 from alcohol 5.
Scheme 6: Proposed mechanism for I2-catalyzed direct nucleophilic substitution of γ-hydroxyallylphosphonate 5...
Scheme 7: Ce(III)-mediated conversion of acetate 7 into γ-aminophosphonates 8a–d.
Beilstein J. Org. Chem. 2016, 12, 2240–2249, doi:10.3762/bjoc.12.216
Graphical Abstract
Figure 1: Bioactive 2,3’-spiropyrrolidinyloxindoles.
Scheme 1: Earlier studied cycloaddition reaction.
Scheme 2: Synthesis of dipolarophiles 1a–c.
Scheme 3: Synthesis of dispirocompounds 4a–o.
Figure 2: Synthesis of dispiro compounds 4a–o. Reaction conditions: heating the mixture of compounds 1 (0.5 m...
Scheme 4: Synthesis of dipolarophiles 1d–f.
Figure 3: Synthesis of dispiro compounds 4p–t. Reaction conditions: heating the solution of compounds 1 (0.5 ...
Figure 4: Key interactions in {1H-13C}HMBC spectrum of 4f.
Figure 5: General view of 4c in the crystal in thermal ellipsoids representation (50% probability). Hydrogen ...
Figure 6: General view of 4e in the crystal in thermal ellipsoids representation (40% probability). Hydrogen ...
Figure 7: General view of 4r in the crystal in thermal ellipsoids representation (50% probability). Hydrogen ...
Figure 8: Modes of approach of azomethine ylide (R = H, Ph).
Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184
Graphical Abstract
Scheme 1: Nitroso hetero-Diels–Alder reaction.
Scheme 2: The hetero-Diels–Alder reaction between thebaine (4) and an acylnitroso dienophile 5.
Figure 1: Examples of nitroso dienophiles frequently used in hetero-Diels–Alder reaction studies.
Scheme 3: Synthesis of arylnitroso species by substitution of a trifluoroborate group [36].
Scheme 4: Synthesis of arylnitroso compounds by amine oxidation.
Scheme 5: Synthesis of arylnitroso compounds by hydroxylamine oxidation.
Scheme 6: Synthesis of chloronitroso compounds by the treatment of a nitronate anion with oxalyl chloride.
Scheme 7: Non-oxidative routes to acylnitroso species.
Figure 2: RB3LYP/6-31G* computed energies (in kcal·mol−1) and bond lengths for exo and endo-transition states...
Scheme 8: Hetero-Diels–Alder cycloadditions of diene 28 and nitroso dienophiles 29.
Figure 3: Relative reactivity (ΔE#) and regioselectivity (Δ) for hetero-Diels–Alder of 28 and nitroso dienoph...
Scheme 9: Reaction of chiral 1-phosphono-1,3-butadiene 31 with nitroso dienophiles 32.
Scheme 10: Hetero-Diels–Alder reactions of hydroxamic acids 35 with various dienes 37.
Scheme 11: General regioselectivity of the nitroso hetero-Diels–Alder reaction observed with unsymmetrical die...
Scheme 12: Effect of the nitroso species on the regioselectivity for weakly directing 2-substituted dienes.
Scheme 13: Regioselectivity of 1,4-disubstituted dienes 51.
Scheme 14: Nitroso hetero-Diels–Alder reaction between Boc-nitroso compound 54 and dienes 55.
Scheme 15: Nitroso hetero-Diels–Alder reaction between Wightman reagent 58 and dienes 59.
Scheme 16: Regioselective reaction of 3-dienyl-2-azetidinones 62 with nitrosobenzene (47).
Scheme 17: The regioselective reaction of 1,3-butadienes 65 with various nitroso heterodienophiles 66.
Scheme 18: Catalysis of the nitroso hetero-Diels–Alder reaction by vanadium in the presence of the oxidant CHP...
Figure 4: 1,2-Oxazines synthesized in solution with moderate to high regioselectivity, showing the favored re...
Figure 5: 1,2-Oxazines synthesized in the solid phase with moderate to high regioselectivity, showing the fav...
Scheme 19: Regioselectivity of solution-phase nitroso hetero-Diels–Alder reaction with acyl and aryl nitroso d...
Scheme 20: Favored regioisomeric outcome for the solution and solid-phase reactions, giving hetero-Diels–Alder...
Figure 6: Favored regioisomers and regioisomeric ratios for 1,2-oxazines synthesized in solid phase (91, 93, ...
Scheme 21: Regiocontrol of the reaction between 3-dienyl-2-azetidinones and nitrosobenzene due to change in a ...
Scheme 22: Regiocontrol of the reaction between diene 111 and 2-methyl-6-nitrosopyridine (112) due to metal co...
Scheme 23: Asymmetric hetero-Diels–Alder reactions reported by Vasella [56].
Scheme 24: Asymmetric hetero-Diels–Alder reaction of cyclohexa-1,3-diene (120) with acylnitroso dienophile 119....
Scheme 25: Asymmetric induction with L-proline derivatives 124–126.
Scheme 26: Asymmetric cycloaddition of the acylnitroso compound 136 to diene 135.
Scheme 27: Asymmetric induction with arylmenthol-based nitroso dienophiles 142.
Scheme 28: Cycloaddition of silyloxycyclohexadiene 145 to the acylnitroso dienophile derived from (+)-camphors...
Scheme 29: Asymmetric reaction of O-isopropylidene-protected cis-cyclohexa-3,5-diene-1,2-diol 147 with mannofu...
Scheme 30: Synthesis of synthon 152 from 2-methoxyphenol 150 and chiral auxiliary 151.
Scheme 31: Asymmetric nitroso hetero-Diels–Alder reaction with Wightman chloronitroso reagent 58.
Scheme 32: Asymmetric 1,2-oxazine synthesis using chiral cyclic diene 157 and the application of this reaction...
Scheme 33: Asymmetric 1,2-oxazine synthesis using a chiral diene reported by Jones et al. [75]. aRegioisomeric rat...
Scheme 34: The nitroso hetero-Diels–Alder reaction of acyclic oxazolidine-substituted diene 170 and chiral 1-s...
Scheme 35: The nitroso hetero-Diels–Alder reaction of acyclic lactam-substituted diene 176 with various acylni...
Scheme 36: The hetero-Diels–Alder reaction of acylnitroso dienophile.
Scheme 37: The hetero-Diels–Alder reaction of arylnitroso dienophiles using Lewis acids.
Scheme 38: Asymmetric hetero-Diels–Alder reactions of chiral alkyl N-dienylpyroglutamates.
Scheme 39: Catalytic asymmetric arylnitroso reaction between mono-substituted 1,3-cyclohexadiene 196 and disub...
Figure 7: Plausible chelate intermediate complexes formed during the hetero-Diels–Alder reaction to give 1,2-...
Scheme 40: Catalytic asymmetric nitroso hetero-Diels–Alder between cyclic dienes and 2-nitrosopyridine.
Scheme 41: The reason for the increased enantioselectivity of stereoisomer 212 compared with stereoisomer 213.
Scheme 42: The copper-catalyzed nitroso hetero-Diels–Alder reaction of 6-methyl-2-nitrosopyridine (199) with p...
Scheme 43: Asymmetric nitroso hetero-Diels–Alder reaction of nitrosoarenes with dienylcarbamates catalyzed by ...
Scheme 44: The enantioselective hetero-Diels–Alder reaction between nitrosobenzene and (E)-2,4-pentadien-1-ol (...
Scheme 45: Asymmetric nitroso hetero-Diels–Alder reaction using tartaric acid ester chelation of the diene and...
Beilstein J. Org. Chem. 2016, 12, 1476–1486, doi:10.3762/bjoc.12.144
Graphical Abstract
Figure 1: Previous (UA1776, UA2201 and UA2209 [7,8]) and new 1a–q phosphonate derivatives designed as potential cN...
Scheme 1: Synthesis of (1-azido-2,5-di-O-acetyl-3-O-benzoyl-6-deoxy-6-diethylphosphono)-β-ribo-(5S)-hexofuran...
Scheme 2: General synthetic pathway for the 1,2,3-triazolo-β-hydroxyphosphonate derivatives.
Figure 2: Black arrow indicates 1H,1H-COSY correlations for compound 2. Green (C1’ and H5) and blue (H1’ and ...
Figure 3: Arrows indicate 1H,1H-NOESY (blue) and 1H,13C-HMBC (green) correlations for compound 3h.
Figure 4: Arrows indicate 1H,1H-NOESY (blue) and 1H,13C-HMBC (green) correlations for compound 3i.
Figure 5: Inhibition of the nucleotidase activity in presence of representative triazole-based derivatives.
Figure 6: Comparison of the docking poses obtained for two active derivatives in the substrate binding site o...
Figure 7: Superimposition of the docking poses obtained for IMP (pink sticks), derivatives 1n (cyan sticks) a...
Figure 8: Comparison of the docking poses obtained for three active derivatives in the substrate binding site...
Beilstein J. Org. Chem. 2016, 12, 239–244, doi:10.3762/bjoc.12.25
Graphical Abstract
Scheme 1: Palladium-catalyzed ring-opening reactions of oxabenzonorbornadiene.
Scheme 2: Palladium-catalyzed ring-opening of 1 with p-iodotoluene.
Scheme 3: Potential regioisomers from the palladium-catalyzed ring-opening reaction of 2 with aryl iodides.
Scheme 4: Palladium-catalyzed ring-opening of C1 substituted oxabenzonorbornadiene.
Scheme 5: Proposed mechanism for the palladium-catalyzed ring-opening reaction of oxanorbornadiene.
Beilstein J. Org. Chem. 2016, 12, 97–109, doi:10.3762/bjoc.12.11
Graphical Abstract
Figure 1: Example of elucidation of 2D NMR spectra of 2-O-Cin-α-CD.
Figure 2: 2D ROESY spectrum of 2-O-Cin-α-CD in D2O at 25 °C at 24 mM concentration.
Figure 3: Expansion of the 2D ROESY spectrum of 2-O-Cin-α-CD indicating the geometric arrangement.
Figure 4: 1H NMR spectra of 2-O-Cin-α-CD in D2O at 25 °C at different concentrations.
Figure 5: 1H NMR spectra of 3-O-Cin-α-CD in D2O at 25 °C recorded at various concentrations.
Figure 6: Diffusion coefficients of 2-O-Cin-α-CD (black) and, 3-O-Cin-α-CD (red) in D2O at various concentrat...
Figure 7: Effect of solvent on the size distribution of aggregates formed by 2-O-Cin-α-CD at 25 °C (the appli...
Figure 8: Effect of a solvent on the size distribution of aggregates formed by 3-O-Cin-α-CD at 25 °C (the app...
Figure 9: Aggregate sizes (diameter) of 2-O-Cin-α-CD (black) and 3-O-Cin-α-CD (red) in water at various tempe...
Figure 10: Schematic representation of the DLS experiment proving the host–guest nature of the aggregate forma...
Figure 11: The effect of competitive additives on the size distribution of aggregates formed by 3-O-Cin-α-CD a...
Figure 12: Expansion of the 2D ROESY spectrum of 2-O-Cin-α-CD in the presence of CioOK as competitive guest mo...
Figure 13: 1H NMR spectrum of 2-O-Cin-α-CD before (up) and after (down) the addition of CioOK in 5-fold molar ...
Figure 14: The influence of 5 mM 2-O-Cin-α-CD in BGE (right column) on the decrease of the effective electroph...
Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280
Graphical Abstract
Scheme 1: Copper-catalyzed asymmetric preparation of biaryl diacids by Ullmann coupling.
Scheme 2: Intramolecular biaryl coupling of bis(iodotrimethoxybenzoyl)hexopyranose derivatives.
Scheme 3: Preparation of 3,3’-disubstituted MeO-BIPHEP derivatives.
Scheme 4: Enantioselective synthesis of trans-4,5,9,10-tetrahydroxy-9,10-dihydrophenanthrene.
Scheme 5: Copper-catalyzed coupling of oxazoline-substituted aromatics to afford biaryl products with high di...
Scheme 6: Total synthesis of O-permethyl-tellimagrandin I.
Scheme 7: Total synthesis of (+)-gossypol.
Scheme 8: Total synthesis of (−)-mastigophorene A.
Scheme 9: Total synthesis of isokotanin.
Scheme 10: Synthesis of dimethyl[7]thiaheterohelicenes.
Scheme 11: Intramolecular coupling with chiral ortho-substituents.
Scheme 12: Chiral 1,3-diol-derived tethers in the diastereoselective synthesis of biaryl compounds.
Scheme 13: Synthesis of chiral unsymmetrically substituted biaryl compounds.
Scheme 14: Atroposelective synthesis of biaryl ligands and natural products by using a chiral diether linker.
Scheme 15: Enantioselective arylation reactions of 2-methylacetoacetates.
Scheme 16: Asymmetric aryl C–N coupling reactions following a desymmetrization strategy.
Scheme 17: Construction of cyano-bearing all-carbon quaternary stereocenters.
Scheme 18: An unexpected inversion of the enantioselectivity in the asymmetric C–N coupling reactions using ch...
Scheme 19: Differentiation of two nucleophilic amide groups.
Scheme 20: Synthesis of spirobilactams through a double N-arylation reaction.
Scheme 21: Asymmetric N-arylation through kinetic resolution.
Scheme 22: Formation of cyano-substituted quaternary stereocenters through kinetic resolution.
Scheme 23: Copper-catalyzed intramolecular desymmetric aryl C–O coupling.
Scheme 24: Transition metal-catalyzed allylic substitutions.
Scheme 25: Copper-catalyzed asymmetric allylic substitution of allyl phosphates.
Scheme 26: Allylic substitution of allyl phosphates with allenylboronates.
Scheme 27: Allylic substitution of allyl phosphates with vinylboron.
Scheme 28: Allylic substitution of allyl phosphates with vinylboron.
Scheme 29: Construction of quaternary stereogenic carbon centers through enantioselective allylic cross-coupli...
Scheme 30: Cu-catalyzed enantioselective allyl–allyl cross-coupling.
Scheme 31: Cu-catalyzed enantioselective allylic substitutions with silylboronates.
Scheme 32: Asymmetric allylic substitution of allyl phosphates with silylboronates.
Scheme 33: Stereoconvergent synthesis of chiral allylboronates.
Scheme 34: Enantioselective allylic substitutions with diboronates.
Scheme 35: Enantioselective allylic alkylations of terminal alkynes.
Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228
Graphical Abstract
Figure 1: Hernandulcin and other bisabolanic derivatives extracted from Lippia dulcis.
Scheme 1: Synthesis of (+)-neoisopulegol. Reagents and conditions: (a) Jones reagent, acetone, 0 °C, 3 h; (b)...
Scheme 2: Reagents and conditions: (a) (i) t-BuOK, BuLi, hexane, −10 °C/rt; 2 h; (ii) BrCH2CH=C(CH3)2; −10°C/...
Scheme 3: Reagents and conditions: (a) cat. methylene blue, light, bubbling O2, CH2Cl2/MeOH 4:1, rt, 15 h; (b...
Scheme 4: Reagents and conditions: (a) (S)-MeCBS or (R)-MeCBS for 15b or 15c, respectively, BH3·Me2S, −78 °C ...
Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218
Graphical Abstract
Figure 1: Cyclic chiral phosphines based on bridged-ring skeletons.
Figure 2: Cyclic chiral phosphines based on binaphthyl skeletons.
Figure 3: Cyclic chiral phosphines based on ferrocene skeletons.
Figure 4: Cyclic chiral phosphines based on spirocyclic skeletons.
Figure 5: Cyclic chiral phosphines based on phospholane ring skeletons.
Figure 6: Acyclic chiral phosphines.
Figure 7: Multifunctional chiral phosphines based on binaphthyl skeletons.
Figure 8: Multifunctional chiral phosphines based on amino acid skeletons.
Scheme 1: Asymmetric [3 + 2] annulations of allenoates with electron-deficient olefins, catalyzed by the chir...
Scheme 2: Asymmetric [3 + 2] annulations of allenoate and enones, catalyzed by the chiral binaphthyl-based ph...
Scheme 3: Asymmetric [3 + 2] annulations of N-substituted olefins and allenoates, catalyzed by the chiral bin...
Scheme 4: Asymmetric [3 + 2] annulations of 2-aryl-1,1-dicyanoethylenes with ethyl allenoate, catalyzed by th...
Scheme 5: Asymmetric [3 + 2] annulations of 3-alkylideneindolin-2-ones with ethyl allenoate, catalyzed by the...
Scheme 6: Asymmetric [3 + 2] annulations of 2,6-diarylidenecyclohexanones with allenoates, catalyzed by the c...
Scheme 7: Asymmetric [3 + 2] annulations of allenoate with alkylidene azlactones, catalyzed by the chiral bin...
Scheme 8: Asymmetric [3 + 2] annulations of C60 with allenoates, catalyzed by the chiral phosphine B6.
Scheme 9: Asymmetric [3 + 2] annulations of α,β-unsaturated esters and ketones with an allenoate, catalyzed b...
Scheme 10: Asymmetric [3 + 2] annulations of exocyclic enones with allenoates, catalyzed by the ferrocene-modi...
Scheme 11: Asymmetric [3 + 2] annulations of enones with an allenylphosphonate, catalyzed by the ferrocene-mod...
Scheme 12: Asymmetric [3 + 2] annulations of 3-alkylidene-oxindoles with ethyl allenoate, catalyzed by the fer...
Scheme 13: Asymmetric [3 + 2] annulations of dibenzylideneacetones with ethyl allenoate, catalyzed by the ferr...
Scheme 14: Asymmetric [3 + 2] annulations of trisubstituted alkenes with ethyl allenoate, catalyzed by the fer...
Scheme 15: Asymmetric [3 + 2] annulations of 2,6-diarylidenecyclohexanones with allenoates, catalyzed by the f...
Scheme 16: Asymmetric [3 + 2] annulations of α,β-unsaturated ketones with ethyl allenoates, catalyzed by the f...
Scheme 17: Asymmetric [3 + 2] annulations of α,β-unsaturated esters with allenoates, catalyzed by the ferrocen...
Scheme 18: Asymmetric [3 + 2] annulations of alkylidene azlactones with allenoates, catalyzed by the chiral sp...
Scheme 19: Asymmetric [3 + 2] annulations of α-trimethylsilyl allenones and electron-deficient olefins, cataly...
Scheme 20: Asymmetric [3 + 2] annulations of α,β-unsaturated ketones with an allenone, catalyzed by the chiral...
Scheme 21: Asymmetric [3 + 2] annulations of cyclic enones with allenoates, catalyzed by the chiral α-amino ac...
Scheme 22: Asymmetric [3 + 2] annulations of arylidenemalononitriles and analogues with an allenoate, catalyze...
Scheme 23: Asymmetric [3 + 2] annulations of α,β-unsaturated esters with an allenoate, catalyzed by the chiral...
Scheme 24: Asymmetric [3 + 2] annulations of 3,5-dimethyl-1H-pyrazole-derived acrylamides with an allenoate, c...
Scheme 25: Asymmetric [3 + 2] annulations of maleimides with allenoates, catalyzed by the chiral phosphine H10....
Scheme 26: Asymmetric [3 + 2] annulations of α-substituted acrylates with allenoate, catalyzed by the chiral p...
Scheme 27: Asymmetric [3 + 2] annulation of an N-tosylimine with an allenoate, catalyzed by the chiral phosphi...
Scheme 28: Asymmetric [3 + 2] annulations of N-tosylimines with an allenoate, catalyzed by the chiral phosphin...
Scheme 29: Asymmetric [3 + 2] annulations of N-tosylimines with an allenoate, catalyzed by the chiral phosphin...
Scheme 30: Asymmetric [3 + 2] annulations of N-diphenylphosphinoyl aromatic imines with butynoates, catalyzed ...
Scheme 31: Asymmetric [3 + 2] annulations of N-tosylimines with allenylphosphonates, catalyzed by the chiral p...
Scheme 32: Asymmetric [3 + 2] annulation of an N-tosylimine with an allenoate, catalyzed by the chiral phosphi...
Scheme 33: Asymmetric [3 + 2] annulations of N-diphenylphosphinoyl aromatic imines with allenoates (top), cata...
Scheme 34: Asymmetric [3 + 2] annulation of N-diphenylphosphinoylimines with allenoates, catalyzed by the chir...
Scheme 35: Asymmetric [3 + 2] annulation of an azomethine imine with an allenoate, catalyzed by the chiral pho...
Scheme 36: Asymmetric [3 + 2] annulations between α,β-unsaturated esters/ketones and 3-butynoates, catalyzed b...
Scheme 37: Asymmetric intramolecular [3 + 2] annulations of electron-deficient alkenes and MBH carbonates, cat...
Scheme 38: Asymmetric [3 + 2] annulations of methyleneindolinone and methylenebenzofuranone derivatives with M...
Scheme 39: Asymmetric [3 + 2] annulations of activated isatin-based alkenes with MBH carbonates, catalyzed by ...
Scheme 40: Asymmetric [3 + 2] annulations of maleimides with MBH carbonates, catalyzed by the chiral phosphine ...
Scheme 41: A series of [3 + 2] annulations of various activated alkenes with MBH carbonates, catalyzed by the ...
Scheme 42: Asymmetric [3 + 2] annulations of an alkyne with isatins, catalyzed by the chiral phosphine F1.
Scheme 43: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine B1.
Scheme 44: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine H5.
Scheme 45: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphines H13 and H12.
Scheme 46: Asymmetric [4 + 2] annulations catalyzed by the chiral phosphine H6.
Scheme 47: Kerrigan’s [2 + 2] annulations of ketenes with imines, catalyzed by the chiral phosphine B7.
Scheme 48: Asymmetric [4 + 1] annulations, catalyzed by the chiral phosphine G6.
Scheme 49: Asymmetric homodimerization of ketenes, catalyzed by the chiral phosphine F5 and F6.
Scheme 50: Aza-MBH/Michael reactions, catalyzed by the chiral phosphine G1.
Scheme 51: Tandem RC/Michael additions, catalyzed by the chiral phosphine H14.
Scheme 52: Intramolecular tandem RC/Michael addition, catalyzed by the chiral phosphine H15.
Scheme 53: Double-Michael addition, catalyzed by the chiral aminophosphine G9.
Scheme 54: Tandem Michael addition/Wittig olefinations, mediated by the chiral phosphine BIPHEP.
Scheme 55: Asymmetric Michael additions, catalyzed by the chiral phosphines H7, H8, and H9.
Scheme 56: Asymmetric γ-umpolung additions, catalyzed by the chiral phosphine A1.
Scheme 57: Asymmetric γ-umpolung additions, catalyzed by the chiral phosphines E2 and E3.
Scheme 58: Intramolecular γ-additions of hydroxy-2-alkynoates, catalyzed by the chiral phosphine D2.
Scheme 59: Intra-/intermolecular γ-additions, catalyzed by the chiral phosphine D2.
Scheme 60: Intermolecular γ-additions, catalyzed by the chiral phosphines B5 and B3.
Scheme 61: Intermolecular γ-additions, catalyzed by the chiral phosphines E6 and B4.
Scheme 62: Asymmetric allylic substitution of MBH acetates, catalyzed by the chiral phosphine G2.
Scheme 63: Allylic substitutions between MBH acetates or carbonates and an array of nucleophiles, catalyzed by...
Scheme 64: Asymmetric acylation of diols, catalyzed by the chiral phosphines E4 and E5.
Scheme 65: Kinetic resolution of secondary alcohols, catalyzed by the chiral phosphine E8 and E9.
Beilstein J. Org. Chem. 2014, 10, 990–995, doi:10.3762/bjoc.10.98
Graphical Abstract
Scheme 1: Synthesis of α-alkylidene-β-hydrazino acid derivatives from MBH adducts.
Scheme 2: Initial investigation.
Scheme 3: Synthesis of 1H-pyrazole 7.
Scheme 4: A plausible mechanism for the formations of 3.