Search for "dienes" in Full Text gives 204 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Beilstein J. Org. Chem. 2018, 14, 1834–1839, doi:10.3762/bjoc.14.156
Graphical Abstract
Scheme 1: Reactions of aryl/hetarylthiochalcones 1a–d with 1,4-naphthoquinone (2b).
Scheme 2: Reactions of thiochalcones 1a–d with 1,4-anthraquinones 2c and 2d.
Figure 1: ORTEP plot [29] of the molecular structure of 4k showing the major conformation of the disordered thiop...
Figure 2: Products of the reactions of thiochalcones 1a and 1b with 1,4-benzoquinone (2a) and of 1a with mena...
Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128
Graphical Abstract
Scheme 1: Strategies to address the issue of sustainability with polyvalent organoiodine reagents.
Scheme 2: Functionalization of ketones and alkenes with IBX.
Scheme 3: Functionalization of pyrroles with DMP.
Scheme 4: Catalytic benzoyloxy-trifluoromethylation reported by Szabó.
Scheme 5: Catalytic benzoyloxy-trifluoromethylation reported by Mideoka.
Scheme 6: Catalytic 1,4-benzoyloxy-trifluoromethylation of dienes.
Scheme 7: Catalytic benzoyloxy-trifluoromethylation of allylamines.
Scheme 8: Catalytic benzoyloxy-trifluoromethylation of enynes.
Scheme 9: Catalytic benzoyloxy-trifluoromethylation of allenes.
Scheme 10: Alkynylation of N-(aryl)imines with EBX for the formation of furans.
Scheme 11: Catalytic benzoyloxy-alkynylation of diazo compounds.
Scheme 12: Catalytic asymmetric benzoyloxy-alkynylation of diazo compounds.
Scheme 13: Catalytic 1,2-benzoyloxy-azidation of alkenes.
Scheme 14: Catalytic 1,2-benzoyloxy-azidation of enamides.
Scheme 15: Catalytic 1,2-benzoyloxy-iodination of alkenes.
Scheme 16: Seminal study with cyclic diaryl-λ3-iodane.
Scheme 17: Synthesis of alkylidenefluorenes from cyclic diaryl-λ3-iodanes.
Scheme 18: Synthesis of alkyne-substituted alkylidenefluorenes.
Scheme 19: Synthesis of phenanthrenes from cyclic diaryl-λ3-iodanes.
Scheme 20: Synthesis of dibenzocarbazoles from cyclic diaryl-λ3-iodanes.
Scheme 21: Synthesis of triazolophenantridines from cyclic diaryl-λ3-iodanes.
Scheme 22: Synthesis of functionalized benzoxazoles from cyclic diaryl-λ3-iodanes.
Scheme 23: Sequential difunctionalization of cyclic diaryl-λ3-iodanes.
Scheme 24: Double Suzuki–Miyaura coupling reaction of cyclic diaryl-λ3-iodanes.
Scheme 25: Synthesis of a δ-carboline from cyclic diaryl-λ3-iodane.
Scheme 26: Synthesis of N-(aryl)carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 27: Synthesis of carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 28: Synthesis of carbazoles and acridines from cyclic diaryl-λ3-iodanes.
Scheme 29: Synthesis of dibenzothiophenes from cyclic diaryl-λ3-iodanes.
Scheme 30: Synthesis of various sulfur heterocycles from cyclic diaryl-λ3-iodanes.
Scheme 31: Synthesis of dibenzothioheterocycles from cyclic diaryl-λ3-iodanes.
Scheme 32: Synthesis of dibenzosulfides and dibenzoselenides from cyclic diaryl-λ3-iodanes.
Scheme 33: Synthesis of dibenzosulfones from cyclic diaryl-λ3-iodanes.
Scheme 34: Seminal study with linear diaryl-λ3-iodanes.
Scheme 35: N-Arylation of benzotriazole with symmetrical diaryl-λ3-iodanes.
Scheme 36: Tandem catalytic C–H/N–H arylation of indoles with diaryl-λ3-iodanes.
Scheme 37: Tandem N-arylation/C(sp2)–H arylation with diaryl-λ3-iodanes.
Scheme 38: Catalytic intermolecular diarylation of anilines with diaryl-λ3-iodanes.
Scheme 39: Catalytic synthesis of diarylsulfides with diaryl-λ3-iodanes.
Scheme 40: α-Arylation of enolates using [bis(trifluoroacetoxy)iodo]arenes.
Scheme 41: Mechanism of the α-arylation using [bis(trifluoroacetoxy)iodo]arene.
Scheme 42: Catalytic nitrene additions mediated by [bis(acyloxy)iodo]arenes.
Scheme 43: Tandem of C(sp3)–H amination/sila-Sonogashira–Hagihara coupling.
Scheme 44: Tandem reaction using a λ3-iodane as an oxidant, a substrate and a coupling partner.
Scheme 45: Synthesis of 1,2-diarylated acrylamidines with ArI(OAc)2.
Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107
Graphical Abstract
Scheme 1: An overview of different chiral iodine reagents or precursors thereof.
Scheme 2: Asymmetric oxidation of sulfides by chiral hypervalent iodine reagents.
Scheme 3: Oxidative dearomatization of naphthol derivatives by Kita et al.
Scheme 4: [4 + 2] Diels–Alder dimerization reported by Birman et al.
Scheme 5: m-CPBA guided catalytic oxidative naphthol dearomatization.
Scheme 6: Oxidative dearomatization of phenolic derivatives by Ishihara et al.
Scheme 7: Oxidative spirocyclization applying precatalyst 11 developed by Ciufolini et al.
Scheme 8: Asymmetric hydroxylative dearomatization.
Scheme 9: Enantioselective oxylactonization reported by Fujita et al.
Scheme 10: Dioxytosylation of styrene (47) by Wirth et al.
Scheme 11: Oxyarylation and aminoarylation of alkenes.
Scheme 12: Asymmetric diamination of alkenes.
Scheme 13: Stereoselective oxyamination of alkenes reported by Wirth et al.
Scheme 14: Enantioselective and regioselective aminofluorination by Nevado et al.
Scheme 15: Fluorinated difunctionalization reported by Jacobsen et al.
Scheme 16: Aryl rearrangement reported by Wirth et al.
Scheme 17: α-Arylation of β-ketoesters.
Scheme 18: Asymmetric α-oxytosylation of carbonyls.
Scheme 19: Asymmetric α-oxygenation and α-amination of carbonyls reported by Wirth et al.
Scheme 20: Asymmetric α-functionalization of ketophenols using chiral quaternary ammonium (hypo)iodite salt re...
Scheme 21: Oxidative Intramolecular coupling by Gong et al.
Scheme 22: α-Sulfonyl and α-phosphoryl oxylation of ketones reported by Masson et al.
Scheme 23: α-Fluorination of β-keto esters.
Scheme 24: Alkynylation of β-ketoesters and amides catalyzed by phase-transfer catalyst.
Scheme 25: Alkynylation of β-ketoesters and dearomative alkynylation of phenols.
Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98
Graphical Abstract
Scheme 1: Tropone (1), tropolone (2) and their resonance structures.
Figure 1: Natural products containing a tropone nucleus.
Figure 2: Possible isomers 11–13 of benzotropone.
Scheme 2: Synthesis of benzotropones 11 and 12.
Scheme 3: Oxidation products of benzotropylium fluoroborate (16).
Scheme 4: Oxidation of 7-bromo-5H-benzo[7]annulene (22).
Scheme 5: Synthesis of 4,5-benzotropone (11) using o-phthalaldehyde (27).
Scheme 6: Synthesis of 4,5-benzotropone (11) starting from oxobenzonorbornadiene 31.
Scheme 7: Acid-catalyzed cleavage of oxo-bridge of 34.
Scheme 8: Synthesis of 4,5-benzotropone (11) from o-xylylene dibromide (38).
Scheme 9: Synthesis of 4,5-benzotropone (11) via the carbene adduct 41.
Scheme 10: Heck coupling strategy for the synthesis of 11.
Scheme 11: Synthesis of benzofulvalenes via carbonyl group of 4,5-benzotropone (11).
Figure 3: Some cycloheptatrienylium cations.
Scheme 12: Synthesis of condensation product 63 and its subsequent oxidative cyclization products.
Figure 4: A novel series of benzo[7]annulenes prepared from 4,5-benzotropone (11).
Scheme 13: Preparation of substituted benzo[7]annulene 72 using the Mukaiyama-Michael reaction.
Figure 5: Possible benzo[7]annulenylidenes 73–75.
Scheme 14: Thermal and photochemical decomposition of 7-diazo-7H-benzo[7]annulene (76) and the trapping of int...
Scheme 15: Synthesis of benzoheptafulvalene 86.
Scheme 16: Synthesis of 7-(diphenylmethylene)-7H-benzo[7]annulene (89).
Scheme 17: Reaction of 4,5-benzotropone (11) with dimethyl diazomethane.
Scheme 18: Synthesis of dihydrobenzomethoxyazocine 103.
Scheme 19: Synthesis and reducibility of benzo-homo-2-methoxyazocines.
Scheme 20: Synthesis of 4,5-benzohomotropones 104 and 115 from 4,5-benzotropones 11 and 113.
Scheme 21: A catalytic deuterogenation of 4,5-benzotropone (11) and synthesis of 5-monosubstituted benzo[7]ann...
Scheme 22: Synthesis of methyl benzo[7]annulenes 131 and 132.
Scheme 23: Ambident reactivity of halobenzo[7]annulenylium cations 133a/b.
Scheme 24: Preparation of benzo[7]annulenylidene–iron complexes 147.
Scheme 25: Synthesis of 1-ethynylbenzotropone (150) and the etheric compound 152 from 4,5-benzotropone (11) wi...
Scheme 26: Thermal decomposition of 4,5-benzotropone (11).
Scheme 27: Reaction of 4,5-benzotropone (11) with 1,2-ethanediol and 1,2-ethanedithiol.
Scheme 28: Conversions of 1-benzosuberone (162) to 2,3-benzotropone (12).
Scheme 29: Synthesis strategies for 2,3-bezotropone (12) using 1-benzosuberones.
Scheme 30: Oxidation-based synthesis of 2,3-benzotropone (12) via 1-benzosuberone (162).
Scheme 31: Synthesis of 2,3-benzotropone (12) from α-tetralone (171) via ring-expansion.
Scheme 32: Preparation of 2,3-benzotropone (12) by using of benzotropolone 174.
Figure 6: Benzoheptafulvenes as condensation products of 2,3-benzotropone (12).
Scheme 33: Conversion of 2,3-benzotropone (12) to tosylhydrazone salt 182 and gem-dichloride 187.
Figure 7: Benzohomoazocines 191–193 and benzoazocines 194–197.
Scheme 34: From 2,3-benzotropone (12) to carbonium ions 198–201.
Scheme 35: Cycloaddition reactions of 2,3-benzotropone (12).
Scheme 36: Reaction of 2,3-benzotropone (12) with various reagents and compounds.
Figure 8: 3,4-Benzotropone (13) and its resonance structure.
Scheme 37: Synthesis of 6,7-benzobicyclo[3.2.0]hepta-3,6-dien-2-one (230).
Figure 9: Photolysis and thermolysis products of 230.
Figure 10: Benzotropolones and their tautomeric structures.
Scheme 38: Synthesis strategies of 4,5-benzotropolone (238).
Scheme 39: Synthesis protocol for 2-hydroxy-4,5-benzotropone (238) using oxazole-benzo[7]annulene 247.
Figure 11: Some quinoxaline and pyrazine derivatives 254–256 prepared from 4,5-benzotropolone (238).
Scheme 40: Nitration product of 4,5-benzotropolone (238) and its isomerization to 1-nitro-naphthoic acid (259)....
Scheme 41: Synthesis protocol for 6-hydroxy-2,3-benzotropone (239) from benzosuberone (162).
Scheme 42: Various reactions via 6-hydroxy-2,3-benzotropone (239).
Scheme 43: Photoreaction of 6-hydroxy-2,3-benzotropone (239).
Scheme 44: Synthesis of 7-hydroxy-2,3-benzotropone (241) from benzosuberone (162).
Scheme 45: Synthesis strategy for 7-hydroxy-2,3-benzotropone (241) from ketone 276.
Scheme 46: Synthesis of 7-hydroxy-2,3-benzotropone (241) from β-naphthoquinone (280).
Scheme 47: Synthesis of 7-hydroxy-2,3-benzotropone (241) from bicyclic endoperoxide 213.
Scheme 48: Synthesis of 7-hydroxy-2,3-benzotropone (241) by ring-closing metathesis.
Figure 12: Various monosubstitution products 289–291 of 7-hydroxy-2,3-benzotropone (241).
Scheme 49: Reaction of 7-hydroxy-2,3-benzotropone (241) with various reagents.
Scheme 50: Synthesis of 4-hydroxy-2,3-benzotropones 174 and 304 from diketones 300/301.
Scheme 51: Catalytic hydrogenation of diketones 300 and 174.
Scheme 52: Synthesis of halo-benzotropones from alkoxy-naphthalenes 306, 307 and 310.
Figure 13: Unexpected byproducts 313–315 during synthesis of chlorobenzotropone 309.
Figure 14: Some halobenzotropones and their cycloadducts.
Scheme 53: Multisep synthesis of 2-chlorobenzotropone 309.
Scheme 54: A multistep synthesis of 2-bromo-benzotropone 26.
Scheme 55: A multistep synthesis of bromo-2,3-benzotropones 311 and 316.
Scheme 56: Oxidation reactions of 8-bromo-5H-benzo[7]annulene (329) with some oxidants.
Scheme 57: Synthesis of 2-bromo-4,5-benzotropone (26).
Scheme 58: Synthesis of 6-chloro-2,3-benzotropone (335) using LiCl and proposed intermediate 336.
Scheme 59: Reaction of 7-bromo-2,3-benzotropone (316) with methylamine.
Scheme 60: Reactions of bromo-2,3-benzotropones 26 and 311 with dimethylamine.
Scheme 61: Reactions of bromobenzotropones 311 and 26 with NaOMe.
Scheme 62: Reactions of bromobenzotropones 26 and 312 with t-BuOK in the presence of DPIBF.
Scheme 63: Cobalt-catalyzed reductive cross-couplings of 7-bromo-2,3-benzotropone (316) with cyclic α-bromo en...
Figure 15: Cycloadduct 357 and its di-π-methane rearrangement product 358.
Scheme 64: Catalytic hydrogenation of 2-chloro-4,5-benzotropone (311).
Scheme 65: Synthesis of dibromo-benzotropones from benzotropones.
Scheme 66: Bromination/dehydrobromination of benzosuberone (162).
Scheme 67: Some transformations of isomeric dibromo-benzotropones 261A/B.
Scheme 68: Transformations of benzotropolone 239B to halobenzotropolones 369–371.
Figure 16: Bromobenzotropolones 372–376 and 290 prepared via bromination/dehydrobromination strategy.
Scheme 69: Synthesis of some halobenzotropolones 289, 377 and 378.
Figure 17: Bromo-chloro-derivatives 379–381 prepared via chlorination.
Scheme 70: Synthesis of 7-iodo-3,4-benzotropolone (382).
Scheme 71: Hydrogenation of bromobenzotropolones 369 and 370.
Scheme 72: Debromination reactions of mono- and dibromides 290 and 375.
Figure 18: Nitratation and oxidation products of some halobenzotropolenes.
Scheme 73: Azo-coupling reactions of some halobenzotropolones 294, 375 and 378.
Figure 19: Four possible isomers of dibenzotropones 396–399.
Figure 20: Resonance structures of tribenzotropone (400).
Scheme 74: Two synthetic pathways for tribenzotropone (400).
Scheme 75: Synthesis of tribenzotropone (400) from dibenzotropone 399.
Scheme 76: Synthesis of tribenzotropone (400) from 9,10-phenanthraquinone (406).
Scheme 77: Synthesis of tribenzotropone (400) from trifluoromethyl-substituted arene 411.
Figure 21: Dibenzosuberone (414).
Figure 22: Reduction products 415 and 416 of tribenzotropone (400).
Figure 23: Structures of tribenzotropone dimethyl ketal 417 and 4-phenylfluorenone (412) and proposed intermed...
Figure 24: Structures of benzylidene- and methylene-9H-tribenzo[a,c,e][7]annulenes 419 and 420 and chiral phos...
Figure 25: Structures of tetracyclic alcohol 422, p-quinone methide 423 and cation 424.
Figure 26: Structures of host molecules 425–427.
Scheme 78: Synthesis of non-helical overcrowded derivatives syn/anti-431.
Figure 27: Hexabenzooctalene 432.
Figure 28: Structures of possible eight isomers 433–440 of naphthotropone.
Scheme 79: Synthesis of naphthotropone 437 starting from 1-phenylcycloheptene (441).
Scheme 80: Synthesis of 10-hydroxy-11H-cyclohepta[a]naphthalen-11-one (448) from diester 445.
Scheme 81: Synthesis of naphthotropone 433.
Scheme 82: Synthesis of naphthotropones 433 and 434 via cycloaddition reaction.
Scheme 83: Synthesis of naphthotropone 434 starting from 452.
Figure 29: Structures of tricarbonyl(tropone)irons 458, and possible cycloadducts 459.
Scheme 84: Synthesis of naphthotropone 436.
Scheme 85: Synthesis of precursor 465 for naphthotropone 435.
Scheme 86: Generation of naphthotropone 435 from 465.
Figure 30: Structures of tropylium cations 469 and 470.
Figure 31: Structures of tropylium ions 471+.BF4−, 472+.BF4−, and 473+.BF4−.
Scheme 87: Synthesis of tropylium ions 471+.BF4− and 479+.ClO4−.
Scheme 88: Synthesis of 1- and 2-methylanthracene (481 and 482) via carbene–carbene rearrangement.
Figure 32: Trapping products 488–490.
Scheme 89: Generation and chemistry of a naphthoannelated cycloheptatrienylidene-cycloheptatetraene intermedia...
Scheme 90: Proposed intermediates and reaction pathways for adduct 498.
Scheme 91: Exited-state intramolecular proton transfer of 505.
Figure 33: Benzoditropones 506 and 507.
Scheme 92: Synthesis of benzoditropone 506e.
Scheme 93: Synthetic approaches for dibenzotropone 507 via tropone (1).
Scheme 94: Formation mechanisms of benzoditropone 507 and 516 via 515.
Scheme 95: Synthesis of benzoditropones 525 and 526 from pyromellitic dianhydride (527).
Figure 34: Possible three benzocyclobutatropones 534–536.
Scheme 96: Synthesis of benzocyclobutatropones 534 and 539.
Scheme 97: Synthesis attempts for benzocyclobutatropone 545.
Scheme 98: Generation and trapping of symmetric benzocyclobutatropone 536.
Scheme 99: Synthesis of chloro-benzocyclobutatropone 552 and proposed mechanism of fluorenone derivatives.
Scheme 100: Synthesis of tropolone analogue 559.
Scheme 101: Synthesis of tropolones 561 and 562.
Figure 35: o/p-Tropoquinone rings (563 and 564) and benzotropoquinones (565–567).
Scheme 102: Synthesis of benzotropoquinone 566.
Scheme 103: Synthesis of benzotropoquinone 567 via a Diels–Alder reaction.
Figure 36: Products 575–577 through 1,2,3-benzotropoquinone hydrate 569.
Scheme 104: Structures 578–582 prepared from tropoquinone 567.
Figure 37: Two possible structures 583 and 584 for dibenzotropoquinone, and precursor compound 585 for 583.
Scheme 105: Synthesis of saddle-shaped ketone 592 using dibenzotropoquinone 584.
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. 2018, 14, 716–733, doi:10.3762/bjoc.14.61
Graphical Abstract
Figure 1: Assembly of catalyst-functionalized amphiphilic block copolymers into polymer micelles and vesicles...
Scheme 1: C–N bond formation under micellar catalyst conditions, no organic solvent involved. Adapted from re...
Scheme 2: Suzuki−Miyaura couplings with, or without, ppm Pd. Conditions: ArI 0.5 mmol 3a, Ar’B(OH)2 (0.75–1.0...
Figure 2: PQS (4a), PQS attached proline catalyst 4b. Adapted from reference [26]. Copyright 2012 American Chemic...
Figure 3: 3a) Schematic representation of a Pickering emulsion with the enzyme in the water phase (i), or wit...
Scheme 3: Cascade reaction with GOx and Myo. Adapted from reference [82].
Figure 4: Cross-linked polymersomes with Cu(OTf)2 catalyst. Reprinted with permission from [15].
Figure 5: Schematic representation of enzymatic polymerization in polymersomes. (A) CALB in the aqueous compa...
Figure 6: Representation of DSN-G0. Reprinted with permission from [100].
Figure 7: The multivalent esterase dendrimer 5 catalyzes the hydrolysis of 8-acyloxypyrene 1,3,6-trisulfonate...
Figure 8: Conversion of 4-NP in five successive cycles of reduction, catalyzed by Au@citrate, Au@PEG and Au@P...
Beilstein J. Org. Chem. 2018, 14, 634–641, doi:10.3762/bjoc.14.50
Graphical Abstract
Scheme 1: Synthesis of macrocyclic derivative 4.
Figure 1: Possible route to sucrose cryptands 6.
Figure 2: Possible route to dienes of type 9.
Scheme 2: Unsuccessful attempts to amines 12a and 13b.
Scheme 3: Syntheses of "elongated" amines 17 and 18.
Scheme 4: Synthesis of macrocycle 25.
Beilstein J. Org. Chem. 2018, 14, 618–625, doi:10.3762/bjoc.14.48
Graphical Abstract
Scheme 1: Bidentate bisborane Lewis acids.
Scheme 2: Complexation reaction of 5,10-dimethyl-5,10-dihydroboranthrene (A) with Lewis bases analyzed by NMR...
Figure 1: Time-dependent 1H NMR spectra of the air-exposed complex B.
Scheme 3: Synthetic procedures of bisboranes A and B.
Figure 2: ORTEP drawing (50% probability) of complex B.
Figure 3: UV–vis spectrum of complex B was measured in CHCl3 and compared with pyridazine and bisborane A (co...
Beilstein J. Org. Chem. 2018, 14, 531–536, doi:10.3762/bjoc.14.39
Graphical Abstract
Scheme 1: Hetero-Diels–Alder (HDA) reactions of N-acylnitroso species.
Scheme 2: DIB-mediated oxidative HDA reactions of 1a–c with various guaiacols.
Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4
Graphical Abstract
Scheme 1: General overview over the sulfur-based substrates and reactive intermediates that are discussed in ...
Scheme 2: Photoredox-catalyzed radical thiol–ene reaction, applying [Ru(bpz)3](PF6)2 as photocatalyst.
Scheme 3: Photoredox-catalyzed thiol–ene reaction of aliphatic thiols with alkenes enabled by aniline derivat...
Scheme 4: Photoredox-catalyzed radical thiol–ene reaction for the postfunctionalization of polymers (a) and n...
Scheme 5: Photoredox-catalyzed thiol–ene reaction enabled by bromotrichloromethane as redox additive.
Scheme 6: Photoredox-catalyzed preparation of β-ketosulfoxides with Eosin Y as organic dye as photoredox cata...
Scheme 7: Greaney’s photocatalytic radical thiol–ene reaction, applying TiO2 nanoparticles as photocatalyst.
Scheme 8: Fadeyi’s photocatalytic radical thiol–ene reaction, applying Bi2O3 as photocatalyst.
Scheme 9: Ananikov’s photocatalytic radical thiol-yne reaction, applying Eosin Y as photocatalyst.
Scheme 10: Organocatalytic visible-light photoinitiated thiol–ene coupling, applying phenylglyoxylic acid as o...
Scheme 11: Xia’s photoredox-catalyzed synthesis of 2,3-disubstituted benzothiophenes, applying 9-mesityl-10-me...
Scheme 12: Wang’s metal-free photoredox-catalyzed radical thiol–ene reaction, applying 9-mesityl-10-methylacri...
Scheme 13: Visible-light benzophenone-catalyzed metal- and oxidant-free radical thiol–ene reaction.
Scheme 14: Visible-light catalyzed C-3 sulfenylation of indole derivatives using Rose Bengal as organic dye.
Scheme 15: Photocatalyzed radical thiol–ene reaction and subsequent aerobic sulfide-oxidation with Rose Bengal...
Scheme 16: Photoredox-catalyzed synthesis of diaryl sulfides.
Scheme 17: Photocatalytic cross-coupling of aryl thiols with aryl diazonium salts, using Eosin Y as photoredox...
Scheme 18: Photocatalyzed cross-coupling of aryl diazonium salts with cysteines in batch and in a microphotore...
Scheme 19: Fu’s [Ir]-catalyzed photoredox arylation of aryl thiols with aryl halides.
Scheme 20: Fu’s photoredox-catalyzed difluoromethylation of aryl thiols.
Scheme 21: C–S cross-coupling of thiols with aryl iodides via [Ir]-photoredox and [Ni]-dual-catalysis.
Scheme 22: C–S cross-coupling of thiols with aryl bromides, applying 3,7-bis-(biphenyl-4-yl)-10-(1-naphthyl)ph...
Scheme 23: Collin’s photochemical dual-catalytic cross-coupling of thiols with bromoalkynes.
Scheme 24: Visible-light-promoted C–S cross-coupling via intermolecular electron donor–acceptor complex format...
Scheme 25: Li’s visible-light photoredox-catalyzed thiocyanation of indole derivatives with Rose Bengal as pho...
Scheme 26: Hajra’s visible-light photoredox-catalyzed thiocyanation of imidazoheterocycles with Eosin Y as pho...
Scheme 27: Wang’s photoredox-catalyzed thiocyanation reaction of indoles, applying heterogeneous TiO2/MoS2 nan...
Scheme 28: Yadav’s photoredox-catalyzed α-C(sp3)–H thiocyanation reaction for tertiary amines, applying Eosin ...
Scheme 29: Yadav’s photoredox-catalyzed synthesis of 5-aryl-2-imino-1,3-oxathiolanes.
Scheme 30: Yadav’s photoredox-catalyzed synthesis of 1,3-oxathiolane-2-thiones.
Scheme 31: Li’s photoredox catalysis for the preparation of 2-substituted benzothiazoles, applying [Ru(bpy)3](...
Scheme 32: Lei’s external oxidant-free synthesis of 2-substituted benzothiazoles by merging photoredox and tra...
Scheme 33: Metal-free photocatalyzed synthesis of 2-aminobenzothiazoles, applying Eosin Y as photocatalyst.
Scheme 34: Metal-free photocatalyzed synthesis of 1,3,4-thiadiazoles, using Eosin Y as photocatalyst.
Scheme 35: Visible-light photoredox-catalyzed preparation of benzothiophenes with Eosin Y.
Scheme 36: Visible-light-induced KOH/DMSO superbase-promoted preparation of benzothiophenes.
Scheme 37: Jacobi von Wangelin’s photocatalytic approach for the synthesis of aryl sulfides, applying Eosin Y ...
Scheme 38: Visible-light photosensitized α-C(sp3)–H thiolation of aliphatic ethers.
Scheme 39: Visible-light photocatalyzed cross-coupling of alkyl and aryl thiosulfates with aryl diazonium salt...
Scheme 40: Visible-light photocatalyzed, controllable sulfenylation and sulfoxidation with organic thiosulfate...
Scheme 41: Rastogi’s photoredox-catalyzed methylsulfoxidation of aryl diazonium salts, using [Ru(bpy)3]Cl2 as ...
Scheme 42: a) Visible-light metal-free Eosin Y-catalyzed procedure for the preparation of vinyl sulfones from ...
Scheme 43: Visible-light photocatalyzed cross-coupling of sodium sulfinates with secondary enamides.
Scheme 44: Wang’s photocatalyzed oxidative cyclization of phenyl propiolates with sulfinic acids, applying Eos...
Scheme 45: Lei’s sacrificial oxidant-free synthesis of allyl sulfones by merging photoredox and transition met...
Scheme 46: Photocatalyzed Markovnikov-selective radical/radical cross-coupling of aryl sulfinic acids and term...
Scheme 47: Visible-light Eosin Y induced cross-coupling of aryl sulfinic acids and styrene derivatives, afford...
Scheme 48: Photoredox-catalyzed bicyclization of 1,7-enynes with sulfinic acids, applying Eosin Y as photocata...
Scheme 49: Visible-light-accelerated C–H-sulfinylation of arenes and heteroarenes.
Scheme 50: Visible-light photoredox-catalyzed β-selenosulfonylation of electron-rich olefins, applying [Ru(bpy)...
Scheme 51: Photocatalyzed preparation of β-chlorosulfones from the respective olefins and p-toluenesulfonyl ch...
Scheme 52: a) Photocatalyzed preparation of β-amidovinyl sulfones from sulfonyl chlorides. b) Preparation of β...
Scheme 53: Visible-light photocatalyzed sulfonylation of aliphatic tertiary amines, applying [Ru(bpy)3](PF6)2 ...
Scheme 54: Reiser’s visible-light photoredox-catalyzed preparation of β-hydroxysulfones from sulfonyl chloride...
Scheme 55: a) Sun’s visible-light-catalyzed approach for the preparation of isoquinolinonediones, applying [fac...
Scheme 56: Visible-light photocatalyzed sulfonylation/cyclization of vinyl azides, applying [Ru(bpy)3]Cl2 as p...
Scheme 57: Visible-light photocatalyzed procedure for the formation of β-ketosulfones from aryl sulfonyl chlor...
Scheme 58: Zheng’s method for the sulfenylation of indole derivatives, applying sulfonyl chlorides via visible...
Scheme 59: Cai’s visible-light induced synthesis of β-ketosulfones from sulfonyl hydrazines and alkynes.
Scheme 60: Photoredox-catalyzed approach for the preparation of vinyl sulfones from sulfonyl hydrazines and ci...
Scheme 61: Jacobi von Wangelin’s visible-light photocatalyzed chlorosulfonylation of anilines.
Scheme 62: Three-component photoredox-catalyzed synthesis of N-amino sulfonamides, applying PDI as organic dye....
Scheme 63: Visible-light induced preparation of complex sulfones from oximes, silyl enol ethers and SO2.
Beilstein J. Org. Chem. 2018, 14, 1–10, doi:10.3762/bjoc.14.1
Graphical Abstract
Scheme 1: Synthetic routes to 2,4,6,8-tetraoxaadamantanes.
Scheme 2: Conversion of dipivaloylketene (2) to bisdioxines (2,6,9-trioxabicyclo[3.3.1]nona-3,7-dienes) 4 and...
Scheme 3: 2,6,9-Trioxabicyclo[3.3.1]nonadienes (bisdioxines, 9–13) derived from dipivaloylketene (2).
Scheme 4: Mechanisms of formation of bisdioxine acid derivatives from dimer 3.
Scheme 5: Recently reported synthesis of chromenobisdioxines.
Scheme 6: Formation of tetraoxaadamantanes.
Scheme 7: Decarboxylative hydrolysis and oxa-Michael-type ring closure.
Scheme 8: Oxime and hydrazine derivatives of bisdioxines and tetraoxaadamantanes.
Figure 1: Bistetraoxaadamantane derivatives.
Scheme 9: Inward-pointing isocyanate, urethane and carbamate groups in bisdioxines. The diisocyanate is obtai...
Scheme 10: Microwave-assisted tetraoxaadamantane formation.
Scheme 11: Cyclic bisdioxine ester derivative 34 forming a single mono-tetraoxaadamantane.
Figure 2: Cyclic bisdioxine derivative not forming a tetraoxaadamantane due to reduced cavity size.
Figure 3: The bisdioxine-calix[6]arene derivative 37 complexes Cs+ but does not form a tetraoxaadamantane der...
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, 2710–2738, doi:10.3762/bjoc.13.269
Graphical Abstract
Scheme 1: Generation of phosphorus ylides from vinylphosphonium salts.
Scheme 2: Intramolecular Wittig reaction with the use of vinylphosphonium salts.
Scheme 3: Alkylation of diphenylvinylphosphine with methyl or benzyl iodide.
Scheme 4: Methylation of isopropenyldiphenylphosphine with methyl iodide.
Scheme 5: Alkylation of phosphines with allyl halide derivatives and subsequent isomerization of intermediate...
Scheme 6: Alkylation of triphenylphosphine with vinyl triflates in the presence of (Ph3P)4Pd.
Scheme 7: Mechanism of alkylation of triphenylphosphine with vinyl triflates in the presence of (Ph3P)4Pd as ...
Scheme 8: β-Elimination of phenol from β-phenoxyethyltriphenylphosphonium bromide.
Scheme 9: β-Elimination of phenol from β-phenoxyethylphosphonium salts in an alkaline environment.
Scheme 10: Synthesis and subsequent dehydrohalogenation of α-bromoethylphosphonium bromide.
Scheme 11: Synthesis of tributylvinylphosphonium iodides via Peterson-type olefination of α-trimethylsilylphos...
Scheme 12: Synthesis of 1-cycloalkenetriphenylphosphonium salts by electrochemical oxidation of triphenylphosp...
Scheme 13: Suggested mechanism for the electrochemical synthesis of 1-cycloalkenetriphenylphosphonium salts.
Scheme 14: Generation of α,β-(dialkoxycarbonyl)vinylphosphonium salts by addition of triphenylphosphine to ace...
Scheme 15: Synthesis of 2-(N-acylamino)vinylphosphonium halides by imidoylation of β-carbonyl ylides with imid...
Scheme 16: Imidoylation of β-carbonyl ylides with imidoyl halides generated in situ.
Scheme 17: Synthesis of 2-benzoyloxyvinylphosphonium bromide from 2-propynyltriphenylphosphonium bromide.
Scheme 18: Synthesis of 2-aminovinylphosphonium salts via nucleophilic addition of amines to 2-propynyltriphen...
Scheme 19: Deacylation of 2-(N-acylamino)vinylphosphonium chlorides to 2-aminovinylphosphonium salts.
Scheme 20: Resonance structures of 2-aminovinylphosphonium salts and tautomeric equilibrium between aminovinyl...
Scheme 21: Synthesis of 2-aminovinylphosphonium salts by reaction of (formylmethyl)triphenylphosphonium chlori...
Scheme 22: Generation of ylides by reaction of vinyltriphenylphosphonium bromide with nucleophiles and their s...
Scheme 23: Intermolecular Wittig reaction with the use of vinylphosphonium bromide and organocopper compounds ...
Scheme 24: Intermolecular Wittig reaction with the use of ylides generated from vinylphosphonium bromides and ...
Scheme 25: Direct transformation of vinylphosphonium salts into ylides in the presence of potassium tert-butox...
Scheme 26: A general method for synthesis of carbo- and heterocyclic systems by the intramolecular Wittig reac...
Scheme 27: Synthesis of 2H-chromene by reaction of vinyltriphenylphosphonium bromide with sodium 2-formylpheno...
Scheme 28: Synthesis of 2,5-dihydro-2,3-dimethylfuran by reaction of vinylphosphonium bromide with 3-hydroxy-2...
Scheme 29: Synthesis of 2H-chromene and 2,5-dihydrofuran derivatives in the intramolecular Wittig reaction wit...
Scheme 30: Enantioselective synthesis of 3,6-dihydropyran derivatives from vinylphosphonium bromide and enanti...
Scheme 31: Synthesis of 2,5-dihydrothiophene derivatives in the intramolecular Wittig reaction from vinylphosp...
Scheme 32: Synthesis of bicyclic pyrrole derivatives in the reaction of vinylphosphonium halides and 2-pyrrolo...
Scheme 33: Stereoselective synthesis of bicyclic 2-pyrrolidinone derivatives in the reaction of vinylphosphoni...
Scheme 34: Stereoselective synthesis of 3-pyrroline derivatives in the intramolecular Wittig reaction from vin...
Scheme 35: Synthesis of cyclic alkenes in the intramolecular Wittig reaction from vinylphosphonium bromide and...
Scheme 36: Synthesis of 1,3-cyclohexadienes by reaction of 1,3-butadienyltriphenylphosphonium bromide with eno...
Scheme 37: Synthesis of bicyclo[3.3.0]octenes by reaction of vinylphosphonium salts with cyclic diketoester.
Scheme 38: Synthesis of quinoline derivatives in the intramolecular Wittig reaction from 2-(2-acylphenylamino)...
Scheme 39: Stereoselective synthesis of γ-aminobutyric acid in the intermolecular Wittig reaction from chiral ...
Scheme 40: Synthesis of allylamines in the intermolecular Wittig reaction from 2-aminovinylphosphonium bromide...
Scheme 41: A general route towards α,β-di(alkoxycarbonyl)vinylphosphonium salts and their subsequent possible ...
Scheme 42: Generation of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with di...
Scheme 43: Synthesis of resonance-stabilized phosphorus ylides in the reaction of triphenylphosphine, dialkyl ...
Scheme 44: Synthesis of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with dia...
Scheme 45: Generation of resonance-stabilized phosphorus ylides in the reaction of acetylenedicarboxylate, tri...
Scheme 46: Synthesis of resonance-stabilized phosphorus ylides via the reaction of dialkyl acetylenedicarboxyl...
Scheme 47: Synthesis of resonance-stabilized ylides derived from semicarbazones, aromatic amides, and 3-(aryls...
Scheme 48: Synthesis of resonance-stabilized ylides via the reaction of triphenylphosphine with dialkyl acetyl...
Scheme 49: Synthesis of resonance-stabilized ylides in the reaction of triphenylphosphine, dialkyl acetylenedi...
Scheme 50: Synthesis of N-acylated α,β-unsaturated γ-lactams via resonance-stabilized phosphorus ylides derive...
Scheme 51: Synthesis of resonance-stabilized phosphorus ylides derived from 6-amino-N,N'-dimethyluracil and th...
Scheme 52: Generation of resonance-stabilized phosphorus ylides in the reaction of triphenylphosphine, dialkyl...
Scheme 53: Synthesis of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with dia...
Scheme 54: Synthesis of 1,3-dienes via intramolecular Wittig reaction with the use of resonance-stabilized yli...
Scheme 55: Synthesis of 1,3-dienes in the intramolecular Wittig reaction from ylides generated from dimethyl a...
Scheme 56: Synthesis of 4-(2-quinolyl)cyclobutene-1,2,3-tricarboxylic acid triesters and isomeric cyclopenteno...
Scheme 57: Synthesis of 4-arylquinolines via resonance-stabilized ylides in the intramolecular Wittig reaction....
Scheme 58: Synthesis of furan derivatives via resonance-stabilized ylides in the intramolecular Wittig reactio...
Scheme 59: Synthesis of 1,3-indanedione derivatives via resonance-stabilized ylides in the intermolecular Witt...
Scheme 60: Synthesis of coumarin derivatives via nucleophilic displacement of the triphenylphosphonium group i...
Scheme 61: Synthesis of 6-formylcoumarin derivatives and their application in the synthesis of dyads.
Scheme 62: Synthesis of di- and tricyclic coumarin derivatives in the reaction of pyrocatechol with two vinylp...
Scheme 63: Synthesis of mono-, di-, and tricyclic derivatives in the reaction of pyrogallol with one or two vi...
Scheme 64: Synthesis of 1,4-benzoxazine derivative by nucleophilic displacement of the triphenylphosphonium gr...
Scheme 65: Synthesis of 7-oxo-7H-pyrido[1,2,3-cd]perimidine derivative via nucleophilic displacement of the tr...
Scheme 66: Application of vinylphosphonium salts in the Diels–Alder reaction with dienes.
Scheme 67: Synthesis of pyrroline derivatives from vinylphosphonium bromide and 5-(4H)-oxazolones.
Scheme 68: Synthesis of pyrrole derivatives in the reactions of vinyltriphenylphosphonium bromide with protona...
Scheme 69: Synthesis of dialkyl 2-(alkylamino)-5-aryl-3,4-furanedicarboxylates via intermediate α,β-di(alkoxyc...
Scheme 70: Synthesis of 1,4-benzoxazine derivatives from acetylenedicarboxylates, phosphines, and 1-nitroso-2-...
Beilstein J. Org. Chem. 2017, 13, 2659–2662, doi:10.3762/bjoc.13.263
Graphical Abstract
Scheme 1: Diels–Alder reaction of isobenzofuran and formation of a benzene ring in the cycloadduct.
Scheme 2: Different approaches for the synthesis of IBF (1).
Scheme 3: Reaction of in situ prepared IBF (1) with DMAD (9).
Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221
Graphical Abstract
Figure 1: Dialkyl dicyanofumarates E-1 and dicyanomaleates Z-1.
Scheme 1: Methods for the synthesis of dialkyl dicyanofumarates E-1 from alkyl cyanoacetates 2.
Scheme 2: Methods for the synthesis of dialkyl dicyanofumarates E-1 from alkyl bromoacetates 3.
Scheme 3: Reaction of dimethyl dicyanofumarate (E-1b) with dimethoxycarbene [(MeO)2C:] generated in situ from...
Scheme 4: Cyclopropanation of diethyl dicyanofumarate (E-1a) through reaction with the thiophene derived sulf...
Scheme 5: Cyclopropanation of dimethyl dicyanofumarate (E-1b) through a stepwise reaction with the in situ ge...
Scheme 6: The [2 + 2]-cycloadditions of dimethyl dicyanofumarate (E-1b) with electron-rich ethylenes 20 and 22...
Scheme 7: The [2 + 2]-cycloaddition of isomeric dimethyl dicyanofumarate (E-1b) and dicyanomaleate (Z-1b) wit...
Scheme 8: Non-concerted [2 + 2]-cycloaddition between E-1b and bicyclo[2.1.0]pentene (27).
Scheme 9: Stepwise [3 + 2]-cycloadditions of some thiocarbonyl S-methanides with dialkyl dicyanofumarates E-1...
Scheme 10: Stepwise [3 + 2]-cycloadditions of dimethyl dicyanofumarate (E-1b) and dimethyl dicyanomaleate (Z-1b...
Scheme 11: [3 + 2]-Cycloaddition of diazomethane with dimethyl dicyanofumarate (E-1b) leading to 1H-pyrazole d...
Scheme 12: Reversible Diels–Alder reaction of fulvenes 36 with diethyl dicyanofumarate (E-1a).
Scheme 13: [4 + 2]-Cycloaddition of 9,10-dimethylanthracene (39b) and E-1a.
Scheme 14: Stepwise [4 + 2]-cycloaddition of dimethyl dicyanofumarate (E-1b) with electron-rich 1,1-dimethoxy-...
Scheme 15: Formal [4 + 2]-cycloaddition of 3,4-di(α-styryl)furan (47) with dimethyl dicyanofumarate (E-1b).
Scheme 16: Acid-catalyzed Michael addition of enolizable ketones of type 49 to E-1.
Scheme 17: Reaction of diethyl dicyanofumarate (E-1a) with ammonia NH3.
Scheme 18: Reaction of dialkyl dicyanofumarates E-1 with primary and secondary amines.
Scheme 19: Reaction of dialkyl dicyanofumarates E-1 with 1-azabicyclo[1.1.0]butanes 55.
Scheme 20: Formation of pyrazole derivatives in the reaction of hydrazines with E-1.
Scheme 21: Formation of 5-aminopyrazole-3,4-dicarboxylate 65 via heterocyclization reactions.
Scheme 22: Reactions of aryl- and hetarylcarbohydrazides 67 with E-1a.
Scheme 23: Multistep reaction leading to perhydroquinoxaline derivative 73.
Scheme 24: Synthesis of ethyl 7-aminopteridin-6-carboxylates 75 via a domino reaction.
Scheme 25: Synthesis of morhpolin-2-ones 80 from E-1 and β-aminoalcohols 78 through an initial aza-Michael add...
Scheme 26: Reaction of 3-amino-5-arylpyrazoles 81 with dialkyl dicyanofumarates E-1 via competitive nucleophil...
Scheme 27: Heterocyclization reaction of thiosemicarbazone 86 with E-1a.
Scheme 28: Formation of diethyl 4-cyano-5-oxotetrahydro-4H-chromene-3,4-dicarboxylate (90) from E-1a via heter...
Scheme 29: Reaction of dialkyl dicyanofumarates E-1 with cysteamine (92).
Scheme 30: Formation of disulfides through reaction of thiols with E-1a.
Scheme 31: Formation of CT salts of E-1 with Mn2+ and Cr2+ metallocenes through one-electron transfer.
Scheme 32: Oxidation of diethyl dicyanofumarate (E-1a) with H2O2 to give oxirane 101.
Scheme 33: The aziridination of E-1b through nitrene addition.
Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215
Beilstein J. Org. Chem. 2017, 13, 1969–1976, doi:10.3762/bjoc.13.192
Graphical Abstract
Scheme 1: Biogenetic hypothesis for the transformation of schkuhriolide (1) into elemanschkuriolide (3).
Figure 1: Reaction paths M (blue), N (orage), O (yellow) and P (green) for the transformation of 1 into 3. Re...
Scheme 2: Similar compounds to melampolide 1 unable to be hemiacetaled.
Figure 2: Schematic representations of the calculated C5 epimeric structures of 2 and 3. Relative electronic ...
Figure 3: Reaction paths of the Cope rearrangements of closed (dark blue and orange) and open (red and pink) ...
Beilstein J. Org. Chem. 2017, 13, 1807–1815, doi:10.3762/bjoc.13.175
Graphical Abstract
Figure 1: Isoprene as chemical building block in nature and organic synthesis.
Scheme 1: Pd-catalyzed dimerization of isoprene.
Scheme 2: Putative mechanism for the Pd(OAc)2-catalyzed dimerization of isoprene.
Scheme 3: Functionalization of the isoprene-dimer 2-TT to substituted O- and N-heterocycles.
Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159
Graphical Abstract
Figure 1: Initial proposal for the core macrolactone structure (left) and the established complete structure ...
Figure 2: Mycolactone congeners and their origins.
Figure 3: Misassigned mycolactone E structure according to Small et al. [50] (11) and the correct structure (6) f...
Figure 4: Schematic illustration of Kishi’s improved mycolactone TLC detection method exploiting derivatizati...
Figure 5: Fluorescent probes derived from natural mycolactone A/B (1a,b) or its synthetic 8-desmethyl analogs...
Figure 6: Tool compounds used by Pluschke and co-workers for elucidating the molecular targets of mycolactone...
Figure 7: Synthetic strategies towards the extended mycolactone core. A) General strategies. B) Kishi’s appro...
Scheme 1: Kishi’s 1st generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 2: Kishi’s 2nd generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 3: Kishi’s 3rd generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 4: Negishi’s synthesis of the extended core structure of mycolactones. Reagents and conditions: a) (i) ...
Scheme 5: Burkart’s (incomplete) 1st generation approach towards the extended core structure of mycolactones....
Scheme 6: Burkart’s (incomplete) 1st, 2nd and 3rd generation approach towards the extended mycolactone core s...
Scheme 7: Altmann’s synthesis of alkyl iodide 91. Reagents and conditions: a) (i) PMB-trichloroacetimidate, T...
Scheme 8: Final steps of Altmann’s synthesis of the extended core structure of mycolactones. Reagents and con...
Scheme 9: Basic principles of the Aggarwal lithiation–borylation homologation process [185,186].
Scheme 10: Aggarwal’s synthesis of the C1–C11 fragment of the mycolactone core. Reagents and conditions: a) Cl...
Scheme 11: Aggarwal’s synthesis of the linear C1–C20 fragment of the mycolactone core. Reagents and conditions...
Figure 8: Synthetic strategies towards the mycolactone A/B lower side chain.
Scheme 12: Gurjar and Cherian’s synthesis of the C1’–C8’ fragment of the mycolactone A/B pentaenoate side chai...
Scheme 13: Gurjar and Cherian’s synthesis of the benzyl-protected mycolactone A/B pentaenoate side chain. Reag...
Scheme 14: Kishi’s synthesis of model compounds for elucidating the stereochemistry of the C7’–C16’ fragment o...
Scheme 15: Kishi’s synthesis of the mycolactone A/B pentaenoate side chain. (a) (i) NaH, (EtO)2P(O)CH2CO2Et, T...
Scheme 16: Feringa and Minnaard's incomplete synthesis of mycolactone A/B pentaenoate side chain. Reagents and...
Scheme 17: Altmann’s approach towards the mycolactone A/B pentaenoate side chain. Reagents and conditions: a) ...
Scheme 18: Negishi’s access to the C1’–C7’ fragment of mycolactone A. Reagents and conditions: a) (i) n-BuLi, ...
Scheme 19: Negishi’s approach to the C1’–C7’ fragment of mycolactone B. Reagents and conditions: a) (i) DIBAL-...
Scheme 20: Negishi’s synthesis of the C8’–C16’ fragment of mycolactone A/B. Reagents and conditions: a) 142, BF...
Scheme 21: Negishi’s assembly of the mycolactone A and B pentaenoate side chains. Reagents and conditions: a) ...
Scheme 22: Blanchard’s approach to the mycolactone A/B pentaenoate side chain. a) (i) Ph3P=C(Me)COOEt, CH2Cl2,...
Scheme 23: Kishi’s approach to the mycolactone C pentaenoate side chain exemplified for the 13’R,15’S-isomer 1...
Scheme 24: Altmann’s (unpublished) synthesis of the mycolactone C pentaenoate side chain. Reagents and conditi...
Scheme 25: Blanchard’s synthesis of the mycolactone C pentaenoate side chain. Reagents and conditions: a) (i) ...
Scheme 26: Kishi’s synthesis of the tetraenoate side chain of mycolactone F exemplified by enantiomer 165. Rea...
Scheme 27: Kishi’s synthesis of the mycolactone E tetraenoate side chain. Reagents and conditions: a) (i) CH2=...
Scheme 28: Wang and Dai’s synthesis of the mycolactone E tetraenoate side chain. Reagents and conditions: a) (...
Scheme 29: Kishi’s synthesis of the dithiane-protected tetraenoate side chain of the minor oxo-metabolite of m...
Scheme 30: Kishi’s synthesis of the mycolactone S1 and S2 pentaenoate side chains. Reagents and conditions: a)...
Scheme 31: Kishi’s 1st generation and Altmann’s total synthesis of mycolactone A/B (1a,b) and Negishi’s select...
Scheme 32: Kishi’s 2nd generation total synthesis of mycolactone A/B (1a,b). Reagents and conditions: a) 2,4,6...
Scheme 33: Blanchard’s synthesis of the 8-desmethylmycolactone core. Reagents and conditions: a) (i) TsCl, TEA...
Scheme 34: Altmann’s (partially unpublished) synthesis of the C20-hydroxylated mycolactone core. Reagents and ...
Scheme 35: Altmann’s and Blanchard’s approaches towards the 11-isopropyl-8-desmethylmycolactone core. Reagents...
Scheme 36: Blanchard’s synthesis of the saturated variant of the C11-isopropyl-8-desmethylmycolactone core. Re...
Scheme 37: Structure elucidation of photo-mycolactones generated from tetraenoate 224.
Scheme 38: Kishi’s synthesis of the linear precursor of the photo-mycolactone B1 lower side chain. Reagents an...
Scheme 39: Kishi’s synthesis of the photo-mycolactone B1 lower side chain. Reagents and conditions: a) LiTMP, ...
Scheme 40: Kishi’s synthesis of a stabilized lower mycolactone side chain. Reagents and conditions: a) (i) TBD...
Scheme 41: Blanchard’s variation of the C12’,C13’,C15’ stereocluster. Reagents and conditions: a) (i) DIBAL-H,...
Scheme 42: Blanchard’s synthesis of aromatic mycolactone polyenoate side chain analogs. Reagents and condition...
Scheme 43: Small’s partial synthesis of a BODIPY-labeled mycolactone derivative and Demangel’s partial synthes...
Scheme 44: Blanchard’s synthesis of the BODIPY-labeled 8-desmethylmycolactones. Reagents and conditions: a) (i...
Scheme 45: Altmann’s synthesis of biotinylated mycolactones. Reagents and conditions: a) (i) CDI, THF, rt, 2 d...
Figure 9: Kishi’s elongated n-butyl carbamoyl mycolactone A/B analog.
Beilstein J. Org. Chem. 2017, 13, 1310–1315, doi:10.3762/bjoc.13.127
Graphical Abstract
Scheme 1: Synthesis route of RAMEB based statistical polyrotaxane.
Figure 1: (a) GPC trace of the polyHEMA-co-polyisoprene polyrotaxane 1 and (b) 500 MHz 1H NMR and DOSY spectr...
Scheme 2: Schematic representation of the synthetic procedure for the preparation of randomly methylated β-CD...
Figure 2: (a) GPC traces of the macroCTA 5 (solid line) and the poly(TRIS-AAm)-b-polyisoprene-b-poly(TRIS-AAm...
Beilstein J. Org. Chem. 2017, 13, 644–647, doi:10.3762/bjoc.13.63
Graphical Abstract
Scheme 1: Top: The natural product deoxynojirimycin and two analogues and marketed drugs Glyset and Zavesca. ...
Scheme 2: Synthesis of Boc- and Pht-protected diene substrates for endoperoxide synthesis. TBA-Cl = tetrabuty...
Scheme 3: Synthesis of endoperoxides 17–19 by [4 + 2]-cycloaddition of dienes 14–16 with singlet oxygen. The ...
Scheme 4: Dihydroxylation and protection of endoperoxides 18 and 19 to provide novel building blocks 20–23 fo...
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, 384–392, doi:10.3762/bjoc.13.41
Graphical Abstract
Scheme 1: Prior and current decarboxylative couplings.
Scheme 2: Esters examined in the decarboxylation reaction.
Scheme 3: Possible mechanistic pathways.
Figure 1: Calculated HOMO of transition state between E and F.
Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30
Graphical Abstract
Scheme 1: Mechanism for the reduction under metal dissolving conditions.
Scheme 2: Example of decyanation in metal dissolving conditions coupled with deprotection [30]. TBDMS = tert-buty...
Scheme 3: Preparation of α,ω-dienes [18,33].
Scheme 4: Cyclization reaction using a radical probe [18].
Scheme 5: Synthesis of (±)-xanthorrhizol (8) [39].
Scheme 6: Mechanism for the reduction of α-aminonitriles by hydride donors.
Scheme 7: Synthesis of phenanthroindolizidines and phenanthroquinolizidines [71].
Scheme 8: Two-step synthesis of 5-unsubstituted pyrrolidines (25 examples and 1 synthetic application, see be...
Scheme 9: Synthesis of (±)-isoretronecanol 19. DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene [74].
Scheme 10: Proposed mechanism with 14a for the NaBH4 induced decyanation reaction (“BH3” = BH3·THF) [74].
Scheme 11: Reductive decyanation by a sodium hydride–iodide composite (26 examples) [81].
Scheme 12: Proposed mechanism for the reduction by NaH [81].
Scheme 13: Reductive decyanation catalyzed by nickel nanoparticles. Yields are given in weight % from GC–MS da...
Scheme 14: Decyanation of 2-cyanobenzo[b]thiophene [87].
Scheme 15: Simplified pathways involved in transition-metal-promoted reductive decyanations [93,95].
Scheme 16: Fe-catalyzed reductive decyanation. Numbers in square brackets represent turnover numbers. The TONs...
Scheme 17: Rh-catalyzed reductive decyanation of aryl nitriles (18 examples, 2 synthetic applications) [103].
Scheme 18: Rh-catalyzed reductive decyanation of aliphatic nitriles (15 examples, one synthetic application) [103].
Scheme 19: Ni-catalyzed reductive decyanation (method A: 28 examples and 2 synthetic applications; method B: 3...
Scheme 20: Reductive decyanation catalyzed by the nickel complex 58 (method A, 14 examples, yield ≥ 20% and 1 ...
Scheme 21: Proposed catalytic cycle for the nickel complex 58 catalyzed decyanation (method A). Only the cycle...
Scheme 22: Synthesis of bicyclic lactones [119,120].
Scheme 23: Reductive decyanation of malononitriles and cyanoacetates using NHC-boryl radicals (9 examples). Fo...
Scheme 24: Proposed mechanism for the reduction by NHC-boryl radicals. The other possible pathway (addition of ...
Scheme 25: Structures of organic electron-donors. Only the major Z isomer of 80 is shown [125,127].
Scheme 26: Reductive decyanation of malononitriles and cyanoacetates using organic electron-donors (method A, ...
Scheme 27: Photoreaction of dibenzylmalononitrile with 81 [128].
Scheme 28: Examples of decyanation promoted in acid or basic media [129,131,134,135].
Scheme 29: Mechanism proposed for the base-induced reductive decyanation of diphenylacetonitriles [136].
Scheme 30: Reductive decyanation of triarylacetonitriles [140].