Search for "acetophenone" in Full Text gives 112 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117
Graphical Abstract
Figure 1: Inherently chiral calix[4]arene-based phase-transfer catalysts.
Scheme 1: Asymmetric alkylations of 3 catalyzed by (±)-1 and (±)-2 under phase-transfer conditions.
Scheme 2: Synthesis of chiral calix[4]arene-based phase-transfer catalyst 7 and structure of O’Donnell’s N-be...
Scheme 3: Asymmetric alkylation of glycine derivative 3 catalyzed by calixarene-based phase-transfer catalyst ...
Figure 2: Calix[4]arene-amides used as phase-transfer catalysts.
Scheme 4: Phase-transfer alkylation of 3 catalyzed by calixarene-triamide 12.
Scheme 5: Synthesis of inherently chiral calix[4]arenes 20a/20b substituted at the lower rim. Reaction condit...
Scheme 6: Asymmetric Henry reaction between 21 and 22 catalyzed by 20a/20b.
Figure 3: Proposed transition state model of asymmetric Henry reaction.
Scheme 7: Synthesis of enantiomerically pure phosphinoferrocenyl-substituted calixarene ligands 27–29.
Scheme 8: Asymmetric coupling reaction of aryl boronates and aryl halides in the presence of calixarene mono ...
Scheme 9: Asymmetric allylic alkylation in the presence of calix[4]arene ligand (S,S)-29.
Figure 4: Structure of inherently chiral oxazoline calix[4]arenes applied in the palladium-catalyzed Tsuji–Tr...
Scheme 10: Asymmetric Tsuji–Trost reaction in the presence of calix[4]arene ligands 36–39.
Figure 5: BINOL-derived calix[4]arene-diphosphite ligands.
Scheme 11: Asymmetric hydrogenation of 41a and 41b catalyzed by in situ-generated catalysts comprised of [Rh(C...
Figure 6: Inherently chiral calix[4]arene 43 containing a diarylmethanol structure.
Scheme 12: Asymmetric Michael addition reaction of 44 with 45 catalyzed by 43.
Figure 7: Calix[4]arene-based chiral primary amine–thiourea catalysts.
Scheme 13: Asymmetric Michael addition of 48 with 49 catalyzed by 47a and 47b.
Scheme 14: Enantioselective Michael addition of 51 to 52 catalyzed by calix[4]arene thioureas.
Scheme 15: Synthesis of calix[4]arene-based tertiary amine–thioureas 54–56.
Scheme 16: Asymmetric Michael addition of 34 and 57 to nitroalkenes 49 catalyzed by 54b.
Scheme 17: Synthesis of p-tert-butylcalix[4]arene bis-squaramide derivative 64.
Scheme 18: Asymmetric Michael addition catalyzed by 64.
Scheme 19: Synthesis of chiral p-tert-butylphenol analogue 68.
Figure 8: Novel prolinamide organocatalysts based on the calix[4]arene scaffold.
Scheme 20: Asymmetric aldol reactions of 72 with 70 and 71 catalyzed by 69b.
Scheme 21: Synthesis of p-tert-butylcalix[4]arene-based chiral organocatalysts 75 and 78 derived from L-prolin...
Scheme 22: Synthesis of upper rim-functionalized calix[4]arene-based L-proline derivative 83.
Scheme 23: Synthesis and proposed structure of Calix-Pro-MN (86).
Figure 9: Calix[4]arene-based L-proline catalysts containing ester, amide and acid units.
Scheme 24: Synthesis of calix[4]arene-based prolinamide 92.
Scheme 25: Calixarene-based catalysts for the aldol reaction of 21 with 70.
Scheme 26: Asymmetric aldol reactions of 72 with cyclic ketones catalyzed by calix[4]arene-based chiral organo...
Figure 10: A proposed structure for catalyst 92 in H2O.
Scheme 27: Synthetic route for organocatalyst 98.
Scheme 28: Asymmetric aldol reactions catalyzed by 99.
Figure 11: Proposed catalytic environment for catalyst 99 in the presence of water.
Scheme 29: Asymmetric aldol reactions between 94 and 72 catalyzed by 55a.
Scheme 30: Enantioselective Biginelli reactions catalyzed by 69f.
Scheme 31: Synthesis of calix[4]arene–(salen) complexes.
Scheme 32: Enantioselective epoxidation of 108 catalyzed by 107a/107b.
Scheme 33: Synthesis of inherently chiral calix[4]arene catalysts 111 and 112.
Scheme 34: Enantioselective MPV reduction.
Scheme 35: Synthesis of chiral calix[4]arene ligands 116a–c.
Scheme 36: Asymmetric MPV reduction with chiral calix[4]arene ligands.
Scheme 37: Chiral AlIII–calixarene complexes bearing distally positioned chiral substituents.
Scheme 38: Asymmetric MPV reduction in the presence of chiral calix[4]arene diphosphites.
Scheme 39: Synthesis of enantiomerically pure inherently chiral calix[4]arene phosphonic acid.
Scheme 40: Asymmetric aza-Diels–Alder reactions catalyzed by (cR,pR)-121.
Scheme 41: Asymmetric ring opening of epoxides catalyzed by (cR,pR)-121.
Beilstein J. Org. Chem. 2018, 14, 992–997, doi:10.3762/bjoc.14.84
Graphical Abstract
Scheme 1: Oxidative intermolecular cross-coupling of dissimilar enolates.
Scheme 2: Scope of the homo- and heterocoupling of enolates. The purple bond indicates the bond formed. The b...
Scheme 3: Study of diastereoselectivity of the cross-coupling reaction.
Beilstein J. Org. Chem. 2018, 14, 734–746, doi:10.3762/bjoc.14.62
Graphical Abstract
Figure 1: Structures of the widespread fungal volatiles oct-1-en-3-ol (1) and 6-pentyl-2H-pyran-2-one (2), th...
Figure 2: Total-ion chromatogram of the bouquet from Hypoxylon invadens MUCL 54175 obtained by the CLSA heads...
Figure 3: Identified volatile organic compounds from Hypoxylon invadens MUCL 54175.
Figure 4: Mass spectra of volatiles from Hypoxylon invadens MUCL 54175. Mass spectra of A) 2,5-dimethylphenol...
Scheme 1: Proposed common biosynthetic pathway to volatile aromatic compounds from Hypoxylon invadens.
Scheme 2: Synthesis of 5-hydroxy-2-methyl-4H-chromen-4-one (19).
Beilstein J. Org. Chem. 2018, 14, 537–546, doi:10.3762/bjoc.14.40
Graphical Abstract
Figure 1: Characterisation of Pd/C electrocatalyst. a) TEM micrograph. b) Energy dispersive X-ray analysis (E...
Figure 2: SEM images of (a) Pd0.02/C/T and (b) Pd0.20/C/T electrodes, with different magnifications.
Figure 3: Cyclic voltammetric behaviour of Pd0.20/C/T electrode in 0.5 M H2SO4. Scan rate: 50 mV s−1. Startin...
Figure 4: Scheme of all components of the electrochemical reactor including reactions involved in both anode ...
Figure 5: Fractional conversion of benzophenone as a function of coulombic passed charge using the PEMER; 0.5...
Figure 6: Plot of cell voltage versus time obtained from a preparative electrosynthesis performed at 10 mA cm...
Figure 7: Fractional conversion of benzophenone as a function of coulombic charge passed; 0.5 M benzophenone ...
Figure 8: Comparison of fractional conversion (XR) and product yield (η) between Pd0.02/C/T, Pd0.20/C/T and Pd...
Figure 9: Fractional conversions of benzophenone and product yield of diphenylmethanol at both electrodes. (a...
Figure 10: (a) General scheme of a PEMER; (b) itemisation of the main parts of PEMER: 1) endplates, 2) gas dif...
Beilstein J. Org. Chem. 2017, 13, 2915–2921, doi:10.3762/bjoc.13.284
Graphical Abstract
Scheme 1: Relative reactivity of α-fluoroacetophenone to α-chloroacetophenone and α-bromoacetophenone.
Scheme 2: Competitive reduction of haloacetophenones and acetophenone.
Figure 1: Conformational energy profiles of halogenated acetophenones (a) in gas phase; (b) in EtOH; (c) over...
Figure 2: Optimised gas phase geometries of (a) α-fluoroacetophenone and (b) α-chloroacetophenone emphasising...
Figure 3: Most stable conformations of (a) α-fluoroacetophenone and (b) α-chloroacetophenone in ethanol.
Figure 4: Expected reactive conformation of halo-acetophenones.
Figure 5: Orbital interactions in gauche- and cis-conformations of haloacetophenones.
Figure 6: Variation of dipole moment with angle for haloacetophenones.
Figure 7: Highest energy conformation of fluoroacetophenone, emphasizing the closeness of approach of fluorin...
Scheme 3: Competitive reduction of fluoroacetone and chloroacetone.
Figure 8: Conformational energy profiles of halogenated acetones in gas phase and in MeOH.
Figure 9: Overlay of conformational energy profiles of fluoroacetone and fluoroacetophenone.
Beilstein J. Org. Chem. 2017, 13, 2854–2861, doi:10.3762/bjoc.13.277
Graphical Abstract
Scheme 1: Beirut reaction.
Scheme 2: Reactivity of 4,6-dinitrobenzofuroxan.
Scheme 3: Reactivity of ANBF (1).
Scheme 4: Synthesis of ANBF.
Scheme 5: Reactions of ANBF with β-dicarbonyl compounds.
Figure 1: General view of molecule 12 in crystal. Anisotropic displacement parameters for non-hydrogen atoms ...
Scheme 6: Reaction of ANBF with 2,4,6-trinitrotoluene.
Figure 2: Partial 1H NMR spectrum of compound 15 in DMSO-d6.
Figure 3: General view of molecule 15 in crystal. Anisotropic displacement parameters for non-hydrogen atoms ...
Scheme 7: Plausible mechanism of adducts formation.
Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273
Graphical Abstract
Scheme 1: Trifluoromethylation of silyl enol ethers.
Scheme 2: Continuous flow trifluoromethylation of ketones under photoredox catalysis.
Scheme 3: Trifluoromethylation of enol acetates.
Scheme 4: Photoredox-catalysed tandem trifluoromethylation/cyclisation of N-arylacrylamides: a route to trifl...
Scheme 5: Tandem trifluoromethylation/cyclisation of N-arylacrylamides using BiOBr nanosheets catalysis.
Scheme 6: Photoredox-catalysed trifluoromethylation/desulfonylation/cyclisation of N-tosyl acrylamides (bpy: ...
Scheme 7: Photoredox-catalysed trifluoromethylation/aryl migration/desulfonylation of N-aryl-N-tosylacrylamid...
Scheme 8: Proposed mechanism for the trifluoromethylation/aryl migration/desulfonylation (/cyclisation) of N-...
Scheme 9: Photoredox-catalysed trifluoromethylation/cyclisation of N-methacryloyl-N-methylbenzamide derivativ...
Scheme 10: Photoredox-catalysed trifluoromethylation/cyclisation of N-methylacryloyl-N-methylbenzamide derivat...
Scheme 11: Photoredox-catalysed trifluoromethylation/dearomatising spirocyclisation of a N-benzylacrylamide de...
Scheme 12: Photoredox-catalysed trifluoromethylation/cyclisation of an unactivated alkene.
Scheme 13: Asymmetric radical aminotrifluoromethylation of N-alkenylurea derivatives using a dual CuBr/chiral ...
Scheme 14: Aminotrifluoromethylation of an N-alkenylurea derivative using a dual CuBr/phosphoric acid catalyti...
Scheme 15: 1,2-Formyl- and 1,2-cyanotrifluoromethylation of alkenes under photoredox catalysis.
Scheme 16: First simultaneous introduction of the CF3 moiety and a Cl atom onto alkenes.
Scheme 17: Chlorotrifluoromethylaltion of terminal, 1,1- and 1,2-substituted alkenes.
Scheme 18: Chorotrifluoromethylation of electron-deficient alkenes (DCE = dichloroethane).
Scheme 19: Cascade trifluoromethylation/cyclisation/chlorination of N-allyl-N-(benzyloxy)methacrylamide.
Scheme 20: Cascade trifluoromethylation/cyclisation (/chlorination) of diethyl 2-allyl-2-(3-methylbut-2-en-1-y...
Scheme 21: Trifluoromethylchlorosulfonylation of allylbenzene derivatives and aliphatic alkenes.
Scheme 22: Access to β-hydroxysulfones from CF3-containing sulfonyl chlorides through a photocatalytic sequenc...
Scheme 23: Cascade trifluoromethylchlorosulfonylation/cyclisation reaction of alkenols: a route to trifluorome...
Scheme 24: First direct C–H trifluoromethylation of arenes and proposed mechanism.
Scheme 25: Direct C–H trifluoromethylation of five- and six-membered (hetero)arenes under photoredox catalysis....
Scheme 26: Alternative pathway for the C–H trifluoromethylation of (hetero)arenes under photoredox catalysis.
Scheme 27: Direct C–H trifluoromethylation of five- and six-membered ring (hetero)arenes using heterogeneous c...
Scheme 28: Trifluoromethylation of terminal olefins.
Scheme 29: Trifluoromethylation of enamides.
Scheme 30: (E)-Selective trifluoromethylation of β-nitroalkenes under photoredox catalysis.
Scheme 31: Photoredox-catalysed trifluoromethylation/cyclisation of an o-azidoarylalkynes.
Scheme 32: Regio- and stereoselective chlorotrifluoromethylation of alkynes.
Scheme 33: PMe3-mediated trifluoromethylsulfenylation by in situ generation of CF3SCl.
Scheme 34: (EtO)2P(O)H-mediated trifluoromethylsulfenylation of (hetero)arenes and thiols.
Scheme 35: PPh3/NaI-mediated trifluoromethylsulfenylation of indole derivatives.
Scheme 36: PPh3/n-Bu4NI mediated trifluoromethylsulfenylation of thiophenol derivatives.
Scheme 37: PPh3/Et3N mediated trifluoromethylsulfinylation of benzylamine.
Scheme 38: PCy3-mediated trifluoromethylsulfinylation of azaarenes, amines and phenols.
Scheme 39: Mono- and dichlorination of carbon acids.
Scheme 40: Monochlorination of (N-aryl-N-hydroxy)acylacetamides.
Scheme 41: Examples of the synthesis of heterocycles fused with β-lactams through a chlorination/cyclisation p...
Scheme 42: Enantioselective chlorination of β-ketoesters and oxindoles.
Scheme 43: Enantioselective chlorination of 3-acyloxazolidin-2-one derivatives (NMM = N-methylmorpholine).
Beilstein J. Org. Chem. 2017, 13, 2179–2185, doi:10.3762/bjoc.13.218
Graphical Abstract
Scheme 1: Spirocyclization of enamines with 5-methoxycarbonyl-1H-pyrrolediones.
Scheme 2: Non-catalyzed spirocyclization of enoles (vinylogous carbonates and carbamates) with 5-methoxycarbo...
Scheme 3: Acid-catalyzed spirocyclization of enoles (vinylogous carboxylates) with 5-alkoxycarbonyl-1H-pyrrol...
Figure 1: ORTEP drawing of compound 12ab (CCDC 1546062) showing 50% probability amplitude displacement ellips...
Scheme 4: Formation of mono-imines and mono-hydrazones of 1,3-cyclohexanediones and tautomeric equilibrium be...
Scheme 5: Spirocyclizations involving non-bulky ketazinones 17 and 5-alkoxycarbonyl-1H-pyrrolediones 9.
Figure 2: ORTEP drawing of compound 21ab (CCDC 1546063) showing 50% probability amplitude displacement ellips...
Figure 3: ORTEP drawing of compound 22a (CCDC 1546065) showing 50% probability amplitude displacement ellipso...
Scheme 6: Spirocyclizations involving bulky ketazinones 22 and 5-alkoxycarbonyl-1H-pyrrolediones 9.
Figure 4: ORTEP drawing of compound 23aa (CCDC 1546064) showing 50% probability amplitude displacement ellips...
Beilstein J. Org. Chem. 2017, 13, 1079–1084, doi:10.3762/bjoc.13.107
Graphical Abstract
Scheme 1: Previous and present approaches.
Scheme 2: Substrate scope. (All of these reactions were carried out on a 2.0 mmol scale using CH3CN (2.0 mL) ...
Scheme 3: Control reactions for clarifying the mechanism.
Scheme 4: Plausible mechanism.
Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48
Graphical Abstract
Figure 1: Biologically active 1-indanones and their structural analogues.
Figure 2: Number of papers about (a) 1-indanones, (b) synthesis of 1-indanones.
Scheme 1: Synthesis of 1-indanone (2) from hydrocinnamic acid (1).
Scheme 2: Synthesis of 1-indanone (2) from 3-(2-bromophenyl)propionic acid (3).
Scheme 3: Synthesis of 1-indanones 5 from 3-arylpropionic acids 4.
Scheme 4: Synthesis of kinamycin (9a) and methylkinamycin C (9b).
Scheme 5: Synthesis of trifluoromethyl-substituted arylpropionic acids 12, 1-indanones 13 and dihydrocoumarin...
Scheme 6: Synthesis of 1-indanones 16 from benzoic acids 15.
Scheme 7: Synthesis of 1-indanones 18 from arylpropionic and 3-arylacrylic acids 17.
Scheme 8: The NbCl5-induced one-step synthesis of 1-indanones 22.
Scheme 9: Synthesis of biologically active 1-indanone derivatives 26.
Scheme 10: Synthesis of enantiomerically pure indatraline ((−)-29).
Scheme 11: Synthesis of 1-indanone (2) from the acyl chloride 30.
Scheme 12: Synthesis of the mechanism-based inhibitors 33 of coelenterazine.
Scheme 13: Synthesis of the indane 2-imidazole derivative 37.
Scheme 14: Synthesis of fluorinated PAHs 41.
Scheme 15: Synthesis of 1-indanones 43 via transition metal complexes-catalyzed carbonylative cyclization of m...
Scheme 16: Synthesis of 6-methyl-1-indanone (46).
Scheme 17: Synthesis of 1-indanone (2) from ester 48.
Scheme 18: Synthesis of benzopyronaphthoquinone 51 from the spiro-1-indanone 50.
Scheme 19: Synthesis of the selective endothelin A receptor antagonist 55.
Scheme 20: Synthesis of 1-indanones 60 from methyl vinyl ketone (57).
Scheme 21: Synthesis of 1-indanones 64 from diethyl phthalate 61.
Scheme 22: Synthesis of 1-indanone derivatives 66 from various Meldrum’s acids 65.
Scheme 23: Synthesis of halo 1-indanones 69.
Scheme 24: Synthesis of substituted 1-indanones 71.
Scheme 25: Synthesis of spiro- and fused 1-indanones 73 and 74.
Scheme 26: Synthesis of spiro-1,3-indanodiones 77.
Scheme 27: Mechanistic pathway for the NHC-catalyzed Stetter–Aldol–Michael reaction.
Scheme 28: Synthesis of 2-benzylidene-1-indanone derivatives 88a–d.
Scheme 29: Synthesis of 1-indanone derivatives 90a–i.
Scheme 30: Synthesis of 1-indanones 96 from o-bromobenzaldehydes 93 and alkynes 94.
Scheme 31: Synthesis of 3-hydroxy-1-indanones 99.
Scheme 32: Photochemical preparation of 1-indanones 103 from ketones 100.
Scheme 33: Synthesis of chiral 3-aryl-1-indanones 107.
Scheme 34: Photochemical isomerization of 2-methylbenzil 108.
Scheme 35: Synthesis of 2-hydroxy-1-indanones 111a–c.
Scheme 36: Synthesis of 1-indanone derivatives 113 and 114 from η6-1,2-dioxobenzocyclobutene complex 112.
Scheme 37: Synthesis of nakiterpiosin (117).
Scheme 38: Synthesis of 2-alkyl-1-indanones 120.
Scheme 39: Synthesis of fluorine-containing 1-indanone derivatives 123.
Scheme 40: Synthesis of 2-benzylidene and 2-benzyl-1-indanones 126, 127 from the chalcone 124.
Scheme 41: Synthesis of 2-bromo-6-methoxy-3-phenyl-1-indanone (130).
Scheme 42: Synthesis of combretastatin A-4-like indanones 132a–s.
Figure 3: Chemical structures of investigated dienones 133 and synthesized cyclic products 134–137.
Figure 4: Chemical structures of 1-indanones and their heteroatom analogues 138–142.
Scheme 43: Synthesis of 2-phosphorylated and 2-non-phosphorylated 1-indanones 147 and 148 from β-ketophosphona...
Scheme 44: Photochemical synthesis of 1-indanone derivatives 150, 153a, 153b.
Scheme 45: Synthesis of polysubstituted-1-indanones 155, 157.
Scheme 46: Synthesis of 1-indanones 159a–g from α-arylpropargyl alcohols 158 using RhCl(PPh3)3 as a catalyst.
Scheme 47: Synthesis of optically active 1-indanones 162 via the asymmetric Rh-catalyzed isomerization of race...
Scheme 48: Mechanism of the Rh-catalyzed isomerization of α-arylpropargyl alcohols 161 to 1-indanones 162.
Figure 5: Chemical structure of abicoviromycin (168) and its new benzo derivative 169.
Scheme 49: Synthesis of racemic benzoabicoviromycin 172.
Scheme 50: Synthesis of [14C]indene 176.
Scheme 51: Synthesis of indanone derivatives 178–180.
Scheme 52: Synthesis of racemic pterosin A 186.
Scheme 53: Synthesis of trans-2,3-disubstituted 1-indanones 189.
Scheme 54: Synthesis of 3-aryl-1-indanone derivatives 192.
Scheme 55: Synthesis of 1-indanone derivatives 194 from 3-(2-iodoaryl)propanonitriles 193.
Scheme 56: Synthesis of 1-indanones 200–204 by cyclization of aromatic nitriles.
Scheme 57: Synthesis of 1,1’-spirobi[indan-3,3’-dione] derivative 208.
Scheme 58: Total synthesis of atipamezole analogues 211.
Scheme 59: Synthesis of 3-[4-(1-piperidinoethoxy)phenyl]spiro[indene-1,1’-indan]-5,5’-diol hydrochloride 216.
Scheme 60: Synthesis of 3-arylindan-1-ones 219.
Scheme 61: Synthesis of 2-hydroxy-1-indanones 222.
Scheme 62: Synthesis of the 1-indanone 224 from the THP/MOM protected chalcone epoxide 223.
Scheme 63: Synthesis of 1-indanones 227 from γ,δ-epoxy ketones 226.
Scheme 64: Synthesis of 2-hydroxy-2-methylindanone (230).
Scheme 65: Synthesis of 1-indanone derivatives 234 from cyclopropanol derivatives 233.
Scheme 66: Synthesis of substituted 1-indanone derivatives 237.
Scheme 67: Synthesis of 7-methyl substituted 1-indanone 241 from 1,3-pentadiene (238) and 2-cyclopentenone (239...
Scheme 68: Synthesis of disubstituted 1-indanone 246 from the siloxydiene 244 and 2-cyclopentenone 239.
Scheme 69: Synthesis of 5-hydroxy-1-indanone (250) via the Diels–Alder reaction of 1,3-diene 248 with sulfoxid...
Scheme 70: Synthesis of halogenated 1-indanones 253a and 253b.
Scheme 71: Synthesis of 1-indanones 257 and 258 from 2-bromocyclopentenones 254.
Scheme 72: Synthesis of 1-indanone 261 from 2-bromo-4-acetoxy-2-cyclopenten-1-one (260) and 1,2-dihydro-4-viny...
Scheme 73: Synthesis of 1-indanone 265 from 1,2-dihydro-7-methoxy-4-vinylnaphthalene (262) and bromo-substitut...
Scheme 74: Synthesis of 1-indanone 268 from dihydro-3-vinylphenanthrene 266 and 4-acetoxy-2-cyclopenten-1-one (...
Scheme 75: Synthesis of 1-indanone 271 from phenylselenyl-substituted cyclopentenone 268.
Scheme 76: Synthesis of 1-indanone 272 from the trienone 270.
Scheme 77: Synthesis of the 1-indanone 276 from the aldehyde 273.
Scheme 78: Synthesis of 1-indanones 278 and 279.
Scheme 79: Synthesis of 1-indanone 285 from octa-1,7-diyne (282) and cyclopentenone 239.
Scheme 80: Synthesis of benz[f]indan-1-one (287) from cyclopentenone 239 and o-bis(dibromomethyl)benzene (286)....
Scheme 81: Synthesis of 3-methyl-substituted benz[f]indan-1-one 291 from o-bis(dibromomethyl)benzene (286) and...
Scheme 82: Synthesis of benz[f]indan-1-one (295) from the anthracene epidioxide 292.
Scheme 83: Synthesis of 1-indanone 299 from homophthalic anhydride 298 and cyclopentynone 297.
Scheme 84: Synthesis of cyano-substituted 1-indanone derivative 301 from 2-cyanomethylbenzaldehyde (300) and c...
Scheme 85: Synthesis of 1-indanone derivatives 303–305 from ketene dithioacetals 302.
Scheme 86: Synthesis of 1-indanones 309–316.
Scheme 87: Mechanism of the hexadehydro-Diels–Alder (HDDA) reaction.
Scheme 88: Synthesis of 1-indenone 318 and 1-indanones 320 and 321 from tetraynes 317 and 319.
Scheme 89: Synthesis of 1-indanone 320 from the triyn 319.
Scheme 90: Synthesis 1-indanone 328 from 2-methylfuran 324.
Scheme 91: Synthesis of 1-indanones 330 and 331 from furans 329.
Scheme 92: Synthesis of 1-indanone 333 from the cycloadduct 332.
Scheme 93: Synthesis of (S)-3-arylindan-1-ones 335.
Scheme 94: Synthesis of (R)-2-acetoxy-1-indanone 338.
Figure 6: Chemical structures of obtained cyclopenta[α]phenanthrenes 339.
Scheme 95: Synthesis of the benzoindanone 343 from arylacetaldehyde 340 with 1-trimethylsilyloxycyclopentene (...
Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31
Graphical Abstract
Figure 1: Graphical representation of (a) conventional flow cell with a saddle-shaped RF coil and (b) flow ca...
Figure 2: Possible geometries of NMR coils.
Figure 3: The NMR pulse sequence used for NOESY with WET solvent suppression [28].
Figure 4: Reaction of p-phenylenediamine with isobutyraldehyde. (a) Flow tube and (b) 1H NMR stacked plot (40...
Figure 5: Scheme and experimental setup of the flow system.
Figure 6: (a) Microfluidic probe. (b) Microreactor holder. (c) Stripline NMR chip holder. (d) Arrangement of ...
Figure 7: Acetylation of benzyl alcohol. Spectra at (a) 9 s and (b) 3 min. Stoichiometry: benzyl alcohol/DIPE...
Figure 8: a) Design of MICCS and b) schematic diagram of MICCS–NMR [45]. CH2Cl2 solutions of oxime ether and trie...
Scheme 1: Proposed reaction mechanism.
Figure 9: Flowsheet of the experimental setup used to study the reaction kinetics of the oligomer formation i...
Figure 10: Design of the experimental setup used to combine on-line NMR spectroscopy and a batch reactor. Repr...
Figure 11: Reaction system 1,3-dimethylurea/formaldehyde. Main reaction pathway and side reactions [47].
Figure 12: (a) Experimental setup for the reaction. (b) Reaction samples analyzed independently by NMR. (c) Pl...
Figure 13: (a) Schematics of two microreactor cohorts of sample fractions. (b) Reaction product concentration ...
Figure 14: NMR analysis of the reaction of benzaldehyde (2 M in CH3CN) and benzylamine (2 M in CH3CN) (1:1), r...
Figure 15: Flow diagram showing the self-optimizing reactor system. Reproduced with permission from reference [50]...
Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162
Graphical Abstract
Figure 1: The named transformations considered in this review.
Scheme 1: The Baeyer–Villiger oxidation.
Scheme 2: The general mechanism of the peracid-promoted Baeyer–Villiger oxidation.
Scheme 3: General mechanism of the Lewis acid-catalyzed Baeyer–Villiger rearrangement.
Scheme 4: The theoretically studied mechanism of the BV oxidation reaction promoted by H2O2 and the Lewis aci...
Scheme 5: Proton movements in the transition states of the Baeyer–Villiger oxidation.
Scheme 6: The dependence of the course of the Baeyer–Villiger oxidation on the type of O–O-bond cleavage in t...
Scheme 7: The acid-catalyzed Baeyer–Villiger oxidation of cyclic epoxy ketones 22.
Scheme 8: Oxidation of isophorone oxide 29.
Scheme 9: Synthesis of acyl phosphate 32 from acyl phosphonate 31.
Scheme 10: Synthesis of aflatoxin B2 (36).
Scheme 11: The Baeyer–Villiger rearrangement of ketones 37 to lactones 38.
Scheme 12: Synthesis of 3,4-dimethoxybenzoic acid (40) via Baeyer–Villiger oxidation.
Scheme 13: Oxone transforms α,β-unsaturated ketones 43 into vinyl acetates 44.
Scheme 14: The Baeyer–Villiger oxidation of ketones 45 using diaryl diselenide and hydrogen peroxide.
Scheme 15: Baeyer–Villiger oxidation of (E)-2-methylenecyclobutanones.
Scheme 16: Oxidation of β-ionone (56) by H2O2/(BnSe)2 with formation of (E)-2-(2,6,6-trimethylcyclohex-1-en-1-...
Scheme 17: The mechanism of oxidation of ketones 58a–f by hydrogen peroxide in the presence of arsonated polys...
Scheme 18: Oxidation of ketone (58b) by H2O2 to 6-methylcaprolactone (59b) catalyzed by Pt complex 66·BF4.
Scheme 19: Oxidation of ketones 67 with H2O2 in the presence of [(dppb}Pt(µ-OH)]22+.
Scheme 20: The mechanism of oxidation of ketones 67 in the presence of [(dppb}Pt(µ-OH)]22+ and H2O2.
Scheme 21: Oxidation of benzaldehydes 69 in the presence of the H2O2/MeReO3 system.
Scheme 22: Oxidation of acetophenones 72 in the presence of the H2O2/MeReO3 system.
Scheme 23: Baeyer–Villiger oxidation of 2-adamantanone (45c) in the presence of Sn-containing mesoporous silic...
Scheme 24: Aerobic Baeyer–Villiger oxidation of ketones 76 using metal-free carbon.
Scheme 25: A regioselective Baeyer-Villiger oxidation of functionalized cyclohexenones 78 into a dihydrooxepin...
Scheme 26: The oxidation of aldehydes and ketones 80 by H2O2 catalyzed by Co4HP2Mo15V3O62.
Scheme 27: The cleavage of ketones 82 with hydrogen peroxide in alkaline solution.
Scheme 28: Oxidation of ketones 85 to esters 86 with H2O2–urea in the presence of KHCO3.
Scheme 29: Mechanism of the asymmetric oxidation of cyclopentane-1,2-dione 87a with the Ti(OiPr)4/(+)DET/t-BuO...
Scheme 30: The oxidation of cis-4-tert-butyl-2-fluorocyclohexanone (93) with m-chloroperbenzoic acid.
Scheme 31: The mechanism of the asymmetric oxidation of 3-substituted cyclobutanone 96a in the presence of chi...
Scheme 32: Enantioselective Baeyer–Villiger oxidation of cyclic ketones 98.
Scheme 33: Regio- and enantioselective Baeyer–Villiger oxidation of cyclic ketones 101.
Scheme 34: The proposed mechanism of the Baeyer–Villiger oxidation of acetal 105f.
Scheme 35: Synthesis of hydroxy-10H-acridin-9-one 117 from tetramethoxyanthracene 114.
Scheme 36: The Baeyer–Villiger oxidation of the fully substituted pyrrole 120.
Scheme 37: The Criegee rearrangement.
Scheme 38: The mechanism of the Criegee reaction of a peracid with a tertiary alcohol 122.
Scheme 39: Criegee rearrangement of decaline ethylperoxoate 127 into ketal 128.
Scheme 40: The ionic cleavage of 2-methoxy-2-propyl perester 129.
Scheme 41: The Criegee rearrangement of α-methoxy hydroperoxide 136.
Scheme 42: Synthesis of enol esters and acetals via the Criegee rearrangement.
Scheme 43: Proposed mechanism of the transformation of 1-hydroperoxy-2-oxabicycloalkanones 147a–d.
Scheme 44: Transformation of 3-hydroxy-1,2-dioxolanes 151 into diketone derivatives 152.
Scheme 45: Criegee rearrangement of peroxide 153 with the mono-, di-, and tri-O-insertion.
Scheme 46: The sequential Criegee rearrangements of adamantanes 157a,b.
Scheme 47: Synthesis of diaryl carbonates 160a–d from triarylmethanols 159a–d through successive oxygen insert...
Scheme 48: The synthesis of sesquiterpenes 162 from ketone 161 with a Criegee rearrangement as one key step.
Scheme 49: Synthesis of trans-hydrindan derivatives 164, 165.
Scheme 50: The Hock rearrangement.
Scheme 51: The general scheme of the cumene process.
Scheme 52: The Hock rearrangement of aliphatic hydroperoxides.
Scheme 53: The mechanism of solvolysis of brosylates 174a–c and spiro cyclopropyl carbinols 175a–c in THF/H2O2....
Scheme 54: The fragmentation mechanism of hydroperoxy acetals 178 to esters 179.
Scheme 55: The acid-catalyzed rearrangement of phenylcyclopentyl hydroperoxide 181.
Scheme 56: The peroxidation of tertiary alcohols in the presence of a catalytic amount of acid.
Scheme 57: The acid-catalyzed reaction of bicyclic secondary alcohols 192 with hydrogen peroxide.
Scheme 58: The photooxidation of 5,6-disubstituted 3,4-dihydro-2H-pyrans 196.
Scheme 59: The oxidation of tertiary alcohols 200a–g, 203a,b, and 206.
Scheme 60: Transformation of functional peroxide 209 leading to 2,3-disubstitued furans 210 in one step.
Scheme 61: The synthesis of carbazoles 213 via peroxide rearrangement.
Scheme 62: The construction of C–N bonds using the Hock rearrangement.
Scheme 63: The synthesis of moiety 218 from 217 which is a structural motif in the antitumor–antibiotic of CC-...
Scheme 64: The in vivo oxidation steps of cholesterol (219) by singlet oxygen.
Scheme 65: The proposed mechanism of the rearrangement of cholesterol-5α-OOH 220.
Scheme 66: Photochemical route to artemisinin via Hock rearrangement of 223.
Scheme 67: The Kornblum–DeLaMare rearrangement.
Scheme 68: Kornblum–DeLaMare transformation of 1-phenylethyl tert-butyl peroxide (225).
Scheme 69: The synthesis 4-hydroxyenones 230 from peroxide 229.
Scheme 70: The Kornblum–DeLaMare rearrangement of peroxide 232.
Scheme 71: The reduction of peroxide 234.
Scheme 72: The Kornblum–DeLaMare rearrangement of endoperoxide 236.
Scheme 73: The rearrangement of peroxide 238 under Kornblum–DeLaMare conditions.
Scheme 74: The proposed mechanism of rearrangement of peroxide 238.
Scheme 75: The Kornblum–DeLaMare rearrangement of peroxides 242a,b.
Scheme 76: The base-catalyzed rearrangements of bicyclic endoperoxides having electron-withdrawing substituent...
Scheme 77: The base-catalyzed rearrangements of bicyclic endoperoxides 249a,b having electron-donating substit...
Scheme 78: The base-catalyzed rearrangements of bridge-head substituted bicyclic endoperoxides 251a,b.
Scheme 79: The Kornblum–DeLaMare rearrangement of hydroperoxide 253.
Scheme 80: Synthesis of β-hydroxy hydroperoxide 254 from endoperoxide 253.
Scheme 81: The amine-catalyzed rearrangement of bicyclic endoperoxide 263.
Scheme 82: The base-catalyzed rearrangement of meso-endoperoxide 268 into 269.
Scheme 83: The photooxidation of 271 and subsequent Kornblum–DeLaMare reaction.
Scheme 84: The Kornblum–DeLaMare rearrangement as one step in the oxidation reaction of enamines.
Scheme 85: The Kornblum–DeLaMare rearrangement of 3,5-dihydro-1,2-dioxenes 284, 1,2-dioxanes 286, and tert-but...
Scheme 86: The Kornblum–DeLaMare rearrangement of epoxy dioxanes 290a–d.
Scheme 87: Rearrangement of prostaglandin H2 292.
Scheme 88: The synthesis of epicoccin G (297).
Scheme 89: The Kornblum–DeLaMare rearrangement used in the synthesis of phomactin A.
Scheme 90: The Kornblum–DeLaMare rearrangement in the synthesis of 3H-quinazolin-4-one 303.
Scheme 91: The Kornblum–DeLaMare rearrangement in the synthesis of dolabriferol (308).
Scheme 92: Sequential transformation of 3-substituted 2-pyridones 309 into 3-hydroxypyridine-2,6-diones 311 in...
Scheme 93: The Kornblum–DeLaMare rearrangement of peroxide 312 into hydroxy enone 313.
Scheme 94: The Kornblum–DeLaMare rearrangement in the synthesis of polyfunctionalized carbonyl compounds 317.
Scheme 95: The Kornblum–DeLaMare rearrangement in the synthesis of (Z)-β-perfluoroalkylenaminones 320.
Scheme 96: The Kornblum–DeLaMare rearrangement in the synthesis of γ-ketoester 322.
Scheme 97: The Kornblum–DeLaMare rearrangement in the synthesis of diterpenoids 326 and 328.
Scheme 98: The synthesis of natural products hainanolidol (331) and harringtonolide (332) from peroxide 329.
Scheme 99: The synthesis of trans-fused butyrolactones 339 and 340.
Scheme 100: The synthesis of leucosceptroid C (343) and leucosceptroid P (344) via the Kornblum–DeLaMare rearra...
Scheme 101: The Dakin oxidation of arylaldehydes or acetophenones.
Scheme 102: The mechanism of the Dakin oxidation.
Scheme 103: A solvent-free Dakin reaction of aromatic aldehydes 356.
Scheme 104: The organocatalytic Dakin oxidation of electron-rich arylaldehydes 358.
Scheme 105: The Dakin oxidation of electron-rich arylaldehydes 361.
Scheme 106: The Dakin oxidation of arylaldehydes 358 in water extract of banana (WEB).
Scheme 107: A one-pot approach towards indolo[2,1-b]quinazolines 364 from indole-3-carbaldehydes 363 through th...
Scheme 108: The synthesis of phenols 367a–c from benzaldehydes 366a-c via acid-catalyzed Dakin oxidation.
Scheme 109: Possible transformation paths of the highly polarized boric acid coordinated H2O2–aldehyde adduct 3...
Scheme 110: The Elbs oxidation of phenols 375 to hydroquinones.
Scheme 111: The mechanism of the Elbs persulfate oxidation of phenols 375 affording p-hydroquinones 376.
Scheme 112: Oxidation of 2-pyridones 380 under Elbs persulfate oxidation conditions.
Scheme 113: Synthesis of 3-hydroxy-4-pyridone (384) via an Elbs oxidation of 4-pyridone (382).
Scheme 114: The Schenck rearrangement.
Scheme 115: The Smith rearrangement.
Scheme 116: Three main pathways of the Schenck rearrangement.
Scheme 117: The isomerization of hydroperoxides 388 and 389.
Scheme 118: Trapping of dioxacyclopentyl radical 392 by oxygen.
Scheme 119: The hypothetical mechanism of the Schenck rearrangement of peroxide 394.
Scheme 120: The autoxidation of oleic acid (397) with the use of labeled isotope 18O2.
Scheme 121: The rearrangement of 18O-labeled hydroperoxide 400 under an atmosphere of 16O2.
Scheme 122: The rearrangement of the oleate-derived allylic hydroperoxides (S)-421 and (R)-425.
Scheme 123: Mechanisms of Schenck and Smith rearrangements.
Scheme 124: The rearrangement and cyclization of 433.
Scheme 125: The Wieland rearrangement.
Scheme 126: The rearrangement of bis(triphenylsilyl) 439 or bis(triphenylgermyl) 441 peroxides.
Scheme 127: The oxidative transformation of cyclic ketones.
Scheme 128: The hydroxylation of cyclohexene (447) in the presence of tungstic acid.
Scheme 129: The oxidation of cyclohexene (447) under the action of hydrogen peroxide.
Scheme 130: The reaction of butenylacetylacetone 455 with hydrogen peroxide.
Scheme 131: The oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 132: The proposed mechanism for the oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 133: The rearrangement of ozonides.
Scheme 134: The acid-catalyzed oxidative rearrangement of malondialdehydes 462 under the action of H2O2.
Scheme 135: Pathways of the Lewis acid-catalyzed cleavage of dialkyl peroxides 465 and ozonides 466.
Scheme 136: The mechanism of the transformation of (tert-butyldioxy)cyclohexanedienones 472.
Scheme 137: The synthesis of Vitamin K3 from 472a.
Scheme 138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Scheme 139: The rearrangement of hydroperoxide 485 to form diketone 486.
Scheme 140: The base-catalyzed rearrangement of cyclic peroxides 488a–g.
Scheme 141: Synthesis of chiral epoxides and aldols from peroxy hemiketals 491.
Scheme 142: The multistep transformation of (R)-carvone (494) to endoperoxides 496a–e.
Scheme 143: The decomposition of anthracene endoperoxide 499.
Scheme 144: Synthesis of esters 503 from aldehydes 501 via rearrangement of peroxides 502.
Scheme 145: Two possible paths for the base-promoted decomposition of α-azidoperoxides 502.
Scheme 146: The Story decomposition of cyclic diperoxide 506a.
Scheme 147: The Story decomposition of cyclic triperoxide 506b.
Scheme 148: The thermal rearrangement of endoperoxides A into diepoxides B.
Scheme 149: The transformation of peroxide 510 in the synthesis of stemolide (511).
Scheme 150: The possible mechanism of the rearrangement of endoperoxide 261g.
Scheme 151: The photooxidation of indene 517.
Scheme 152: The isomerization of ascaridole (523).
Scheme 153: The isomerization of peroxide 525.
Scheme 154: The thermal transformation of endoperoxide 355.
Scheme 155: The photooxidation of cyclopentadiene (529) at a temperature higher than 0 °C.
Scheme 156: The thermal rearrangement of endoperoxides 538a,b.
Scheme 157: The transformation of peroxides 541.
Scheme 158: The thermal rearrangements of strained cyclic peroxides.
Scheme 159: The thermal rearrangement of diacyl peroxide 551 in the synthesis of C4-epi-lomaiviticin B core 553....
Scheme 160: The 1O2 oxidation of tryptophan (554) and rearrangement of dioxetane intermediate 555.
Scheme 161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Scheme 162: The proposed mechanism of the Fe(II)-promoted rearrangement of 557a–c.
Scheme 163: The reaction of dioxolane 563 with Fe(II) sulfate.
Scheme 164: Fe(II)-promoted rearrangement of 1,2-dioxane 565.
Scheme 165: Fe(II) cysteinate-promoted rearrangement of 1,2-dioxolane 568.
Scheme 166: The transformation of 1,2-dioxanes 572a–c under the action of FeCl2.
Scheme 167: Fe(II) cysteinate-promoted transformation of tetraoxane 574.
Scheme 168: The CoTPP-catalyzed transformation of bicyclic endoperoxides 600a–d.
Scheme 169: The CoTPP-catalyzed transformation of epoxy-1,2-dioxanes.
Scheme 170: The Ru(II)-catalyzed reactions of 1,4-endoperoxide 261g.
Scheme 171: The Ru(II)-catalyzed transformation as a key step in the synthesis of elyiapyrone A (610) from 1,4-...
Scheme 172: Peroxides with antimalarial activity.
Scheme 173: The interaction of iron ions with artemisinin (616).
Scheme 174: The interaction of FeCl2 with 1,2-dioxanes 623, 624.
Scheme 175: The mechanism of reaction 623 and 624 with Fe(II)Cl2.
Scheme 176: The reaction of bicyclic natural endoperoxides G3-factors 631–633 with FeSO4.
Scheme 177: The transformation of terpene cardamom peroxide 639.
Scheme 178: The different ways of the cleavage of tetraoxane 643.
Scheme 179: The LC–MS analysis of interaction of tetraoxane 646 with iron(II)heme 647.
Scheme 180: The rearrangement of 3,6-epidioxy-1,10-bisaboladiene (EDBD, 649).
Scheme 181: Easily oxidized substrates.
Scheme 182: Biopathway of synthesis of prostaglandins.
Scheme 183: The reduction and rearrangements of isoprostanes.
Scheme 184: The partial mechanism for linoleate 658 oxidation.
Scheme 185: The transformation of lipid hydroperoxide.
Scheme 186: The acid-catalyzed cleavage of the product from free-radical oxidation of cholesterol (667).
Scheme 187: Two pathways of catechols oxidation.
Scheme 188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme...
Scheme 189: Carotinoides 679 cleavage by carotenoid cleavage dioxygenases.
Beilstein J. Org. Chem. 2016, 12, 1185–1195, doi:10.3762/bjoc.12.114
Graphical Abstract
Figure 1: Structural motifs of phospinooxazoline ligands.
Scheme 1: Retrosynthetic analysis for NeoPHOX ligands.
Scheme 2: Synthesis of 1st generation NeoPHOX Ir-complexes [19].
Figure 2: Asymmetric hydrogenation with iridium-NeoPHOX catalysts [19].
Figure 3: Employing L-valine as a starting material for C5 substituted oxazoline.
Scheme 3: Synthesis of a C(5)-disubstituted NeoPHOX-Ir complex.
Figure 4: Retrosynthetic analysis for NeoPHOX ligands derived from serine and threonine.
Scheme 4: Revisited synthetic strategy for the preparation of a threonine-based NeoPHOX ligand.
Scheme 5: Undesired β-lactam formation.
Scheme 6: Synthetic strategy for the synthesis of the serine-derived NeoPHOX ligand.
Scheme 7: Derivatization of the 2nd generation NeoPHOX ligands and formation of their iridium complexes.
Figure 5: Crystal structures of selected Ir-complexes. Hydrogen atoms, COD and BArF anions were omitted for c...
Scheme 8: Asymmetric palladium-catalyzed allylic substitution with rac-(E)-1,3-diphenylallyl acetate.
Scheme 9: Asymmetric palladium-catalyzed allylic substitution with rac-(E)-1,3-dimethylallyl acetate.
Scheme 10: Asymmetric palladium-catalyzed allylic substitution with a cyclic substrate.
Beilstein J. Org. Chem. 2016, 12, 1072–1078, doi:10.3762/bjoc.12.101
Graphical Abstract
Scheme 1: Selected benzothiadaiazine 1,1-dioxides with potent biological activities.
Scheme 2: Scope of acetophenones (reaction conditions: 1 (0.33 mmol), 2a (0.3 mmol), DMSO (2 mL), I2 (0.75 eq...
Scheme 3: Scope of 2-aminobenzenesulfonamides (reaction conditions: 1 (0.33 mmol), 2a (0.3 mmol), DMSO (2 mL)...
Scheme 4: Reactions of 2-aminobenzenesulfonamides bearing an alknyl group (reaction conditions: 1 (0.33 mmol)...
Scheme 5: Gram scale reaction between 1a and 2a.
Figure 1: X-ray crystal structure of 4b (CCDC 1444753).
Scheme 6: Control experiment.
Scheme 7: Proposed mechanism.
Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98
Graphical Abstract
Figure 1: 3-Hydroxyoxindole-containing natural products and biologically active molecules.
Scheme 1: Chiral CNN pincer Pd(II) complex 1 catalyzed asymmetric allylation of isatins.
Scheme 2: Asymmetric allylation of ketimine catalyzed by the chiral CNN pincer Pd(II) complex 2.
Scheme 3: Pd/L1 complex-catalyzed asymmetric allylation of 3-O-Boc-oxindoles.
Scheme 4: Cu(OTf)2-catalyzed asymmetric direct addition of acetonitrile to isatins.
Scheme 5: Chiral tridentate Schiff base/Cu complex catalyzed asymmetric Friedel–Crafts alkylation of isatins ...
Scheme 6: Guanidine/CuI-catalyzed asymmetric alkynylation of isatins with terminal alkynes.
Scheme 7: Asymmetric intramolecular direct hydroarylation of α-ketoamides.
Scheme 8: Plausible catalytic cycle for the direct hydroarylation of α-ketoamides.
Scheme 9: Ir-catalyzed asymmetric arylation of isatins with arylboronic acids.
Scheme 10: Enantioselective decarboxylative addition of β-ketoacids to isatins.
Scheme 11: Ruthenium-catalyzed hydrohydroxyalkylation of olefins and 3-hydroxy-2-oxindoles.
Scheme 12: Proposed catalytic mechanism and stereochemical model.
Scheme 13: In-catalyzed allylation of isatins with stannylated reagents.
Scheme 14: Modified protocol for the synthesis of allylated 3-hydroxyoxindoles.
Scheme 15: Hg-catalyzed asymmetric allylation of isatins with allyltrimethylsilanes.
Scheme 16: Enantioselective additions of organoborons to isatins.
Scheme 17: Asymmetric aldol reaction of isatins with cyclohexanone.
Scheme 18: Enantioselective aldol reactions of aliphatic aldehydes with isatin derivatives and the plausible t...
Scheme 19: Enantioselective aldol reaction of isatins and 2,2-dimethyl-1,3-dioxan-5-one.
Scheme 20: Asymmetric aldol reactions between ketones and isatins.
Scheme 21: Phenylalanine lithium salt-catalyzed asymmetric synthesis of 3-alkyl-3-hydroxyoxindoles.
Scheme 22: Aldolization between isatins and dihydroxyacetone derivatives.
Scheme 23: One-pot asymmetric synthesis of convolutamydine A.
Scheme 24: Asymmetric aldol reactions of cyclohexanone and acetone with isatins.
Scheme 25: Aldol reactions of acetone with isatins.
Scheme 26: Aldol reactions of ketones with isatins.
Scheme 27: Enantioselective allylation of isatins.
Scheme 28: Asymmetric aldol reaction of trifluoromethyl α-fluorinated β-keto gem-diols with isatins.
Scheme 29: Plausible mechanism proposed for the asymmetric aldol reaction.
Scheme 30: Asymmetric aldol reaction of 1,1-dimethoxyacetone with isatins.
Scheme 31: Enantioselective Friedel-Crafts reaction of phenols with isatins.
Scheme 32: Enantioselective addition of 1-naphthols with isatins.
Scheme 33: Enantioselective aldol reaction between 3-acetyl-2H-chromen-2-ones and isatins.
Scheme 34: Stereoselective Mukaiyama–aldol reaction of fluorinated silyl enol ethers with isatins.
Scheme 35: Asymmetric vinylogous Mukaiyama–aldol reaction between 2-(trimethylsilyloxy)furan and isatins.
Scheme 36: β-ICD-catalyzed MBH reactions of isatins with maleimides.
Scheme 37: β-ICD-catalyzed MBH reactions of 7-azaisatins with maleimides and activated alkenes.
Scheme 38: Enantioselective aldol reaction of isatins with ketones.
Scheme 39: Direct asymmetric vinylogous aldol reactions of allyl ketones with isatins.
Scheme 40: Enantioselective aldol reactions of ketones with isatins.
Scheme 41: The MBH reaction of isatins with α,β-unsaturated γ-butyrolactam.
Scheme 42: Reactions of tert-butyl hydrazones with isatins followed by oxidation.
Scheme 43: Aldol reactions of isatin derivatives with ketones.
Scheme 44: Enantioselective decarboxylative cyanomethylation of isatins.
Scheme 45: Catalytic kinetic resolution of 3-hydroxy-3-substituted oxindoles.
Scheme 46: Lewis acid catalyzed Friedel–Crafts alkylation of 3-hydroxy-2-oxindoles with electron-rich phenols.
Scheme 47: Lewis acid catalyzed arylation of 3-hydroxyoxindoles with aromatics.
Scheme 48: Synthetic application of 3-arylated disubstituted oxindoles in the construction of core structures ...
Scheme 49: CPA-catalyzed dearomatization and arylation of 3-indolyl-3-hydroxyoxindoles with tryptamines and 3-...
Scheme 50: CPA-catalyzed enantioselective decarboxylative alkylation of β-keto acids with 3-hydroxy-3-indolylo...
Scheme 51: BINOL-derived imidodiphosphoric acid-catalyzed enantioselective Friedel–Crafts reactions of indoles...
Scheme 52: CPA-catalyzed enantioselective allylation of 3-indolylmethanols.
Scheme 53: 3-Indolylmethanol-based substitution and cycloaddition reactions.
Scheme 54: CPA-catalyzed asymmetric [3 + 3] cycloaddtion reactions of 3-indolylmethanols with azomethine ylide...
Scheme 55: CPA-catalyzed three-component cascade Michael/Pictet–Spengler reactions of 3-indolylmethanols and a...
Scheme 56: Acid-promoted chemodivergent and stereoselective synthesis of diverse indole derivatives.
Scheme 57: CPA-catalyzed asymmetric formal [3 + 2] cycloadditions.
Scheme 58: CPA-catalyzed enantioselective cascade reactions for the synthesis of C7-functionlized indoles.
Scheme 59: Lewis acid-promoted Prins cyclization of 3-allyl-3-hydroxyoxindoles with aldehydes.
Scheme 60: Ga(OTf)3-catalyzed reactions of allenols and phenols.
Scheme 61: I2-catalyzed construction of pyrrolo[2.3.4-kl]acridines from enaminones and 3-indolyl-3-hydroxyoxin...
Scheme 62: CPA-catalyzed asymmetric aza-ene reaction of 3-indolylmethanols with cyclic enaminones.
Scheme 63: Asymmetric α-alkylation of aldehydes with 3-indolyl-3-hydroxyoxindoles.
Scheme 64: Organocatalytic asymmetric α-alkylation of enolizable aldehydes with 3-indolyl-3-hydroxyoxindoles a...
Beilstein J. Org. Chem. 2016, 12, 813–824, doi:10.3762/bjoc.12.80
Graphical Abstract
Scheme 1: Synthesis of racemic tetrahydro-2H-pyran-2,4-diols rac-5 from enolates 2 and aldehydes 3.
Scheme 2: Synthesis of rac-5a–j and monoaldol products 6a–i and 6ac–ic as obtained from propiophenone (1a) in...
Figure 1: Crystal structure of enantiopure 5a [40].
Scheme 3: Reaction of various ketones (1b−i) with benzaldehyde (3a) in the presence of InCl3 and ZrCl4.
Figure 2: (a) Crystal structure of 7h and (b) its arrangement in the crystal [43].
Scheme 4: Reaction of n-butyrophenone (1f) with various aldehydes (3b−d) in presence of InCl3 (reaction time:...
Scheme 5: Domino aldol reactions of different aldehydes and ketones possessing p-H, p-F and p-MeO substituent...
Scheme 6: DFT calculations on the formation of A3, hydrolysis of which provides 5a, at M06/6-31G(d)/LANL2DZ//...
Scheme 7: The follow-up reactions of A2OH and 6a at M06/6-31G(d)//B3LYP/6-31G(d) level (ΔGrel with unscaled z...
Scheme 8: Proposed mechanism for the formation of benzaldehyde in the reaction of 9-anthracenylaldehyde (3f) ...
Beilstein J. Org. Chem. 2016, 12, 172–178, doi:10.3762/bjoc.12.19
Graphical Abstract
Scheme 1: Dual-gold-catalysed hydrophenoxylation of alkynes.
Scheme 2: Exploring the functional group tolerance. Reaction conditions: 1a (0.50 mmol, 1 equiv), 2a–o (0.55 ...
Scheme 3: Hydrophenoxylation using polyphenols. Reaction conditions: 1a (1 mmol, 2 equiv), 2p–s (0.50 mmol, 1...
Scheme 4: Hydrophenoxylation of (un)symmetrical alkynes. Reaction conditions: 1b–k (0.50 mmol, 1 equiv), 2t (...
Scheme 5: Regioselective hydrophenoxylation of unsymmetrical alkynes. Reaction conditions: 1l–p (1 equiv), 2a...
Beilstein J. Org. Chem. 2015, 11, 1786–1795, doi:10.3762/bjoc.11.194
Graphical Abstract
Scheme 1: Synthesis of complexes 1 and 2.
Figure 1: Structural view of 1 showing 30% thermal ellipsoids. All hydrogen atoms and PF6− were omitted for c...
Figure 2: Structural view of 2 showing 30% thermal ellipsoids. All hydrogen atoms and PF6− were omitted for c...
Scheme 2: Synthesis of 3.
Figure 3: Structural view of 3 showing 50% thermal ellipsoids. All hydrogen atoms and PF6− were omitted for c...
Scheme 3: Synthesis of complexes 4 and 5.
Figure 4: Structural view of 4 showing 30% thermal ellipsoids. All hydrogen atoms and PF6− were omitted for c...
Figure 5: Structural view of 5 showing 30% thermal ellipsoids. All hydrogen atoms and PF6− were omitted for c...
Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173
Graphical Abstract
Figure 1: Production and utilization of h+ and e– by photoactivation of a semiconductor.
Figure 2: Photoredox activity of TiO2 with moist air.
Scheme 1: TiO2 promoted oxidation of phenanthrene [29].
Scheme 2: SCPC assisted additions of allylic compounds to diazines and imines [40-42].
Scheme 3: TiO2 promoted addition and addition–cyclization reactions of tert-amines with electron-deficient al...
Scheme 4: Reactions of amines promoted by Pt-TiO2 [48,49].
Scheme 5: P25 Promoted alkylations of N-phenylmaleimide with diverse carboxylic acids [53,54]. aAccompanied by R–R d...
Scheme 6: SCPC cyclizations of aryloxyacetic acids with suitably sited alkene acceptors [54]. aYields in brackets...
Scheme 7: TiO2 promoted reactions of aryloxyacetic acids with maleic anhydride and maleimides [53,54].
Scheme 8: Photoredox addition–cyclization reactions of aryloxyacetic and related acids promoted by maleimide [63]....
Scheme 9: SCPC promoted homo-couplings and macrocyclizations with carboxylic acids [64].
Scheme 10: TiO2 promoted alkylations of alkenes with silanes [66] and thiols [67].
Scheme 11: TiO2 reduction of a nitrochromenone derivative [70].
Scheme 12: TiO2 mediated hydrodehalogenations and cyclizations of organic iodides [71].
Scheme 13: TiO2 promoted hydrogenations of maleimides, maleic anhydride and aromatic aldehydes [79].
Scheme 14: Mechanistic sketch of SCPC hydrogenation of aryl aldehydes.
Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134
Graphical Abstract
Figure 1: Pharmaceutical structures targeted in early flow syntheses.
Scheme 1: Flow synthesis of 6-hydroxybuspirone (9). Inserted photograph reprinted with permission from [45]. Copy...
Figure 2: Configuration of a baffled reactor tube (left) and its schematic working principle (right).
Scheme 2: McQuade’s flow synthesis of ibuprofen (16).
Scheme 3: Jamison’s flow synthesis of ibuprofen sodium salt (17).
Scheme 4: Flow synthesis of imatinib (23).
Scheme 5: Flow synthesis of the potent 5HT1B antagonist 28.
Scheme 6: Flow synthesis of a selective δ-opioid receptor agonist 33.
Scheme 7: Flow synthesis of a casein kinase I inhibitor library (38).
Scheme 8: Flow synthesis of fluoxetine (46).
Scheme 9: Flow synthesis of artemisinin (55).
Scheme 10: Telescoped flow synthesis of artemisinin (55) and derivatives (62–64).
Scheme 11: Flow approach towards AZD6906 (65).
Scheme 12: Pilot scale flow synthesis of key intermediate 73.
Scheme 13: Semi-flow synthesis of vildagliptine (77).
Scheme 14: Pilot scale asymmetric flow hydrogenation towards 83. Inserted photograph reprinted with permission...
Figure 3: Schematic representation of the ‘tube-in-tube’ reactor.
Scheme 15: Flow synthesis of fanetizole (87) via tube-in-tube system.
Scheme 16: Flow synthesis of diphenhydramine.HCl (92).
Scheme 17: Flow synthesis of rufinamide (95).
Scheme 18: Large scale flow synthesis of rufinamide precursor 102.
Scheme 19: First stage in the flow synthesis of meclinertant (103).
Scheme 20: Completion of the flow synthesis of meclinertant (103).
Scheme 21: Flow synthesis of olanzapine (121) utilising inductive heating techniques.
Scheme 22: Flow synthesis of amitriptyline·HCl (127).
Scheme 23: Flow synthesis of E/Z-tamoxifen (132) using peristaltic pumping modules.
Figure 4: Container sized portable mini factory (photograph credit: INVITE GmbH, Leverkusen Germany).
Scheme 24: Flow synthesis of imidazo[1,2-a]pyridines 136 linked to frontal affinity chromatography (FAC).
Figure 5: Structures of zolpidem (142) and alpidem (143).
Scheme 25: Synthesis and screening loops in the discovery of new Abl kinase inhibitors.
Figure 6: Schotten–Baumann approach towards LY573636.Na (147).
Scheme 26: Pilot scale flow synthesis of LY2886721 (146).
Scheme 27: Continuous flow manufacture of alikiren hemifumarate 152.
Beilstein J. Org. Chem. 2015, 11, 1000–1007, doi:10.3762/bjoc.11.112
Graphical Abstract
Figure 1: Natural and synthetic derivatives of thieno[2,3-b]indole.
Scheme 1: Synthetic routes to thieno[2,3-b]indoles.
Scheme 2: Synthesis and thionation of indodin-2-ones 11.
Scheme 3: Synthetic paths to thieno[2,3-b]indole 12a. LR = Lawesson's reagent
Figure 2: Mercury [34] representation of the X-ray crystal structure of 12a. Thermal ellipsoids of 50% probabilit...
Scheme 4: Two-step synthesis of 2-(hetero)aryl substituted thieno[2,3-b]indoles 12.
Scheme 5: Synthesis of mono- and dibromo-substituted thieno[2,3-b]indoles 12n,o.
Beilstein J. Org. Chem. 2015, 11, 906–912, doi:10.3762/bjoc.11.102
Graphical Abstract
Figure 1: Selected examples for biologically active 4-hydroxy-2H-chromen-2-one and 4-hydroxy-2(1H)-quinolinon...
Scheme 1: Possible mechanism for the carboxylative cyclization of o-acetamidoacetophenone.
Scheme 2: Cross carboxylative cyclization reaction.
Beilstein J. Org. Chem. 2015, 11, 884–892, doi:10.3762/bjoc.11.99
Graphical Abstract
Figure 1: Tetrahydroquinoline alkaloids of Galipea officinalis.
Scheme 1: Enaminone-based synthesis of (S)-cuspareine.
Scheme 2: The approaches to 2-aroylmethylidene-1,2,3,4-tetrahydroquinolines 1.
Scheme 3: The retrosynthetic analysis of the starting substrates for C–N cross-coupling.
Scheme 4: The synthesis of methyl 3-phenylpropionates. Conditions: (a) piperidine, PhCOOH, toluene, reflux 4 ...
Scheme 5: The synthesis of the starting β-enaminones. Conditions: (a) H2SO4, 65 °C, 46 h; (b) 1. t-BuOK/THF, ...
Figure 2: Ligands for C–N cross-coupling used in this work.
Figure 3: Deprotection of the hydroxy group in 1c to give the Galipein precursor 1e.
Figure 4: ORTEP (50% probability level) view for compound 1a. For selected parameters see Supporting Information File 1.
Beilstein J. Org. Chem. 2015, 11, 213–218, doi:10.3762/bjoc.11.23
Graphical Abstract
Figure 1: Mechanism of reductive aldol–lactonization reaction of maleate with a carbonyl and silane under cop...
Figure 2: Possible copper-catalyzed reductive aldol–lactonization reaction of acrylate with a keto ester and ...
Figure 3: The elimination reactions of lactones.
Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312
Graphical Abstract
Scheme 1: The Grignard-based synthesis of 6-alkyl phenanthridine.
Scheme 2: Radical-mediated synthesis of 6-arylphenanthridine [14].
Scheme 3: A t-BuO• radical-assisted homolytic aromatic substitution mechanism proposed for the conversion of ...
Scheme 4: Synthesis of 5,6-unsubstituted phenanthridine starting from 2-iodobenzyl chloride and aniline [17].
Scheme 5: Phenanthridine synthesis initiated by UV-light irradiation photolysis of acetophenone O-ethoxycarbo...
Scheme 6: PhI(OAc)2-mediated oxidative cyclization of 2-isocyanobiphenyls with CF3SiMe3 [19,20].
Scheme 7: Targeting 6-perfluoroalkylphenanthridines [21,22].
Scheme 8: Easily accessible biphenyl isocyanides reacting under mild conditions (room temp., visible light ir...
Scheme 9: Microwave irradiation of Diels–Alder adduct followed by UV irradiation of dihydrophenanthridines yi...
Scheme 10: A representative palladium catalytic cycle.
Scheme 11: The common Pd-catalyst for the biphenyl conjugation results simultaneously in picolinamide-directed...
Scheme 12: Pd(0)-mediated cyclisation of imidoyl-selenides forming 6-arylphenanthridine derivatives [16]. The inse...
Scheme 13: Palladium-catalysed phenanthridine synthesis.
Scheme 14: Aerobic domino Suzuki coupling combined with Michael addition reaction in the presence of a Pd(OAc)2...
Scheme 15: Rhodium-catalysed alkyne [2 + 2 + 2] cycloaddition reactions [36].
Scheme 16: The O-acetyloximes derived from 2′-arylacetophenones underwent N–O bond cleavage and intramolecular ...
Scheme 17: C–H arylation with aryl chloride in the presence of a simple diol complex with KOt-Bu (top) [39]; for s...
Scheme 18: The subsequent aza-Claisen rearrangement, ring-closing enyne metathesis and Diels–Alder reaction – ...
Scheme 19: Phenanthridine central-ring cyclisation with simultaneous radical-driven phosphorylation [42].
Scheme 20: Three component reaction yielding the benzo[a]phenanthridine core in excellent yields [44].
Scheme 21: a) Reaction of malononitrile and 1,3-indandione with BEP to form the cyclised DPP products; b) pH c...
Figure 1: Schematic presentation of the intercalative binding mode by the neighbour exclusion principle and i...
Figure 2: Urea and guanidine derivatives of EB with modified DNA interactions [57].
Figure 3: Structure of mono- (3) and bis-biguanide (4) derivative. Fluorescence (y-axis normalised to startin...
Scheme 22: Bis-phenanthridinium derivatives (5–7; inert aliphatic linkers, R = –(CH2)4– or –(CH2)6–): rigidity...
Figure 4: Series of amino acid–phenanthridine building blocks (general structure 10; R = H; Gly) and peptide-...
Figure 5: General structure of 45 bis-ethidium bromide analogues. Reproduced with permission from [69]. Copyright...
Scheme 23: Top: Recognition of poly(U) by 12 and ds-polyAH+ by 13; bottom: Recognition of poly(dA)–poly(dT) by ...
Figure 6: The bis-phenanthridinium–adenine derivative 15 (LEFT) showed selectivity towards complementary UMP;...
Figure 7: The neomycin–methidium conjugate targeting DNA:RNA hybrid structures [80].
Figure 8: Two-colour RNA intercalating probe for cell imaging applications: Left: Chemical structure of EB-fl...
Figure 9: The ethidium bromide nucleosides 17 (top) and 18 (bottom). DNA duplex set 1 and 2 (E = phenanthridi...
Figure 10: Left: various DNA duplexes; DNA1 and DNA2 used to study the impact on the adjacent basepair type on...
Figure 11: Structure of 4,9-DAP derivative 19; Rright: MIAPaCa-2 cells stained with 10 μM 19 after 60 and 120 ...
Figure 12: Examples of naturally occurring phenanthridine analogues.