Search for "BINAP" in Full Text gives 69 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265
Graphical Abstract
Scheme 1: Scaled industrial processes for the synthesis of simple pyridines.
Scheme 2: Synthesis of nicotinic acid from 2-methyl-5-ethylpyridine (1.11).
Scheme 3: Synthesis of 3-picoline and nicotinic acid.
Scheme 4: Synthesis of 3-picoline from 2-methylglutarodinitrile 1.19.
Scheme 5: Picoline-based synthesis of clarinex (no yields reported).
Scheme 6: Mode of action of proton-pump inhibitors and structures of the API’s.
Scheme 7: Hantzsch-like route towards the pyridine rings in common proton pump inhibitors.
Figure 1: Structures of rosiglitazone (1.40) and pioglitazone (1.41).
Scheme 8: Synthesis of rosiglitazone.
Scheme 9: Syntheses of 2-pyridones.
Scheme 10: Synthesis and mechanism of 2-pyrone from malic acid.
Scheme 11: Polymer-assisted synthesis of rosiglitazone.
Scheme 12: Synthesis of pioglitazone.
Scheme 13: Meerwein arylation reaction towards pioglitazone.
Scheme 14: Route towards pioglitazone utilising tyrosine.
Scheme 15: Route towards pioglitazone via Darzens ester formation.
Scheme 16: Syntheses of the thiazolidinedione moiety.
Scheme 17: Synthesis of etoricoxib utilising Negishi and Stille cross-coupling reactions.
Scheme 18: Synthesis of etoricoxib via vinamidinium condensation.
Figure 2: Structures of nalidixic acid, levofloxacin and moxifloxacin.
Scheme 19: Synthesis of moxifloxacin.
Scheme 20: Synthesis of (S,S)-2,8-diazabicyclo[4.3.0]nonane 1.105.
Scheme 21: Synthesis of levofloxacin.
Scheme 22: Alternative approach to the levofloxacin core 1.125.
Figure 3: Structures of nifedipine, amlodipine and clevidipine.
Scheme 23: Mg3N2-mediated synthesis of nifedipine.
Scheme 24: Synthesis of rac-amlodipine as besylate salt.
Scheme 25: Aza Diels–Alder approach towards amlodipine.
Scheme 26: Routes towards clevidipine.
Figure 4: Examples of piperidine containing drugs.
Figure 5: Discovery of tiagabine based on early leads.
Scheme 27: Synthetic sequences to tiagabine.
Figure 6: Structures of solifenacin (2.57) and muscarine (2.58).
Scheme 28: Enantioselective synthesis of solifenacin.
Figure 7: Structures of DPP-4 inhibitors of the gliptin-type.
Scheme 29: Formation of inactive diketopiperazines from cis-rotameric precursors.
Figure 8: Co-crystal structure of carmegliptin bound in the human DPP-4 active site (PDB 3kwf).
Scheme 30: Improved route to carmegliptin.
Figure 9: Structures of lamivudine and zidovudine.
Scheme 31: Typical routes accessing uracil, thymine and cytosine.
Scheme 32: Coupling between pyrimidones and riboses via the Vorbrüggen nucleosidation.
Scheme 33: Synthesis of lamivudine.
Scheme 34: Synthesis of raltegravir.
Scheme 35: Mechanistic studies on the formation of 3.22.
Figure 10: Structures of selected pyrimidine containing drugs.
Scheme 36: General preparation of pyrimidines and dihydropyrimidones.
Scheme 37: Synthesis of imatinib.
Scheme 38: Flow synthesis of imatinib.
Scheme 39: Syntheses of erlotinib.
Scheme 40: Synthesis of erlotinib proceeding via Dimroth rearrangement.
Scheme 41: Synthesis of lapatinib.
Scheme 42: Synthesis of rosuvastatin.
Scheme 43: Alternative preparation of the key aldehyde towards rosuvastatin.
Figure 11: Structure comparison between nicotinic acetylcholine receptor agonists.
Scheme 44: Syntheses of varenicline and its key building block 4.5.
Scheme 45: Synthetic access to eszopiclone and brimonidine via quinoxaline intermediates.
Figure 12: Bortezomib bound in an active site of the yeast 20S proteasome ([114], pdb 2F16).
Scheme 46: Asymmetric synthesis of bortezomib.
Figure 13: Structures of some prominent piperazine containing drugs.
Figure 14: Structural comparison between the core of aplaviroc (4.35) and a type-1 β-turn (4.36).
Scheme 47: Examplary synthesis of an aplaviroc analogue via the Ugi-MCR.
Scheme 48: Syntheses of azelastine (5.1).
Figure 15: Structures of captopril, enalapril and cilazapril.
Scheme 49: Synthesis of cilazapril.
Figure 16: Structures of lamotrigine, ceftriaxone and azapropazone.
Scheme 50: Synthesis of lamotrigine.
Scheme 51: Alternative synthesis of lamotrigine (no yields reported).
Figure 17: Structural comparison between imiquimod and the related adenosine nucleoside.
Scheme 52: Conventional synthesis of imiquimod (no yields reported).
Scheme 53: Synthesis of imiquimod.
Scheme 54: Synthesis of imiquimod via tetrazole formation (not all yields reported).
Figure 18: Structures of various anti HIV-medications.
Scheme 55: Synthesis of abacavir.
Figure 19: Structures of diazepam compared to modern replacements.
Scheme 56: Synthesis of ocinaplon.
Scheme 57: Access to zaleplon and indiplon.
Scheme 58: Different routes towards the required N-methylpyrazole 6.65 of sildenafil.
Scheme 59: Polymer-supported reagents in the synthesis of key aminopyrazole 6.72.
Scheme 60: Early synthetic route to sildenafil.
Scheme 61: Convergent preparations of sildenafil.
Figure 20: Comparison of the structures of sildenafil, tadalafil and vardenafil.
Scheme 62: Short route to imidazotriazinones.
Scheme 63: Alternative route towards vardenafils core imidazotriazinone (6.95).
Scheme 64: Bayer’s approach to the vardenafil core.
Scheme 65: Large scale synthesis of vardenafil.
Scheme 66: Mode of action of temozolomide (6.105) as methylating agent.
Scheme 67: Different routes to temozolomide.
Scheme 68: Safer route towards temozolomide.
Figure 21: Some unreported heterocyclic scaffolds in top market drugs.
Beilstein J. Org. Chem. 2013, 9, 2250–2264, doi:10.3762/bjoc.9.264
Graphical Abstract
Figure 1: Gold-promoted 1,2-acyloxy migration on propargylic systems.
Scheme 1: Gold-catalyzed enantioselective intermolecular cyclopropanation.
Scheme 2: Gold-catalyzed enantioselective intramolecular cyclopropanation.
Scheme 3: Gold-catalyzed cyclohepta-annulation cascade.
Scheme 4: Application to the formal synthesis of frondosin A.
Scheme 5: Gold(I)-catalyzed enantioselective cyclopropenation of alkynes.
Scheme 6: Enantioselective cyclopropanation of diazooxindoles.
Figure 2: Proposed structures for gold-activated allene complexes.
Scheme 7: Gold-catalyzed enantioselective [2 + 2] cycloadditions of allenenes.
Scheme 8: Gold-catalyzed allenediene [4 + 3] and [4 + 2] cycloadditions.
Scheme 9: Gold-catalyzed enantioselective [4 + 2] cycloadditions of allenedienes.
Scheme 10: Gold-catalyzed enantioselective [4 + 3] cycloadditions of allenedienes.
Scheme 11: Gold-catalyzed enantioselective [4 + 2] cycloadditions of allenamides.
Scheme 12: Enantioselective [2 + 2] cycloadditions of allenamides.
Scheme 13: Mechanistic rational for the gold-catalyzed [2 + 2] cycloadditions.
Scheme 14: Enantioselective cascade cycloadditions between allenamides and oxoalkenes.
Scheme 15: Enantioselective [3 + 2] cycloadditions of nitrones and allenamides.
Scheme 16: Enantioselective formal [4 + 3] cycloadditions leading to 1,2-oxazepane derivatives.
Scheme 17: Enantioselective gold(I)-catalyzed 1,3-dipolar [3 + 3] cycloaddition between 2-(1-alkynyl)-2-alken-...
Scheme 18: Enantioselective [4 + 3] cycloaddition leading to 5,7-fused bicyclic furo[3,4-d][1,2]oxazepines.
Beilstein J. Org. Chem. 2013, 9, 1202–1209, doi:10.3762/bjoc.9.136
Graphical Abstract
Figure 1: Representative examples of carbazoles with hole-transport, host or luminescent properties.
Scheme 1: Synthetic access to N-arylated carbazoles.
Scheme 2: Proposed mechanistic motivation towards the formation of 3a.
Figure 2: FID chromatogram of the reaction mixture. Only the most intense peaks were structurally assigned. x...
Figure 3: Substrate scope. All reactions were performed using iodonium salt 1 (0.35 mmol), 1.2 equiv of prima...
Scheme 3: Synthesis of dibenzo[b,d]bromolium trifluoromethanesulfonate (6).
Scheme 4: Dibenzo[b,d]bromolium trifluoromethanesulfonate (6) and p-fluoroaniline (2f) to construct carbazole ...
Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34
Graphical Abstract
Scheme 1: Variation of substrates for carbomagnesiation and carbozincation in this article.
Scheme 2: Copper-catalyzed arylmagnesiation and allylmagnesiation of alkynyl sulfone.
Scheme 3: Copper-catalyzed four-component reaction of alkynyl sulfoxide with alkylzinc reagent, diiodomethane...
Scheme 4: Rhodium-catalyzed reaction of aryl alkynyl ketones with arylzinc reagents.
Scheme 5: Allylmagnesiation of propargyl alcohol, which provides the anti-addition product.
Scheme 6: Negishi’s total synthesis of (Z)-γ-bisabolene by allylmagnesiation.
Scheme 7: Iron-catalyzed syn-carbomagnesiation of propargylic or homopropargylic alcohol.
Scheme 8: Mechanism of iron-catalyzed carbomagnesiation.
Scheme 9: Regio- and stereoselective manganese-catalyzed allylmagnesiation.
Scheme 10: Vinylation and alkylation of arylacetylene-bearing hydroxy group.
Scheme 11: Arylmagnesiation of (2-pyridyl)silyl-substituted alkynes.
Scheme 12: Synthesis of tamoxifen from 2g.
Scheme 13: Controlling regioselectivity of carbocupration by attaching directing groups.
Scheme 14: Rhodium-catalyzed carbozincation of ynamides.
Scheme 15: Synthesis of 4-pentenenitriles through carbometalation followed by aza-Claisen rearrangement.
Scheme 16: Uncatalyzed carbomagnesiation of cyclopropenes.
Scheme 17: Iron-catalyzed carbometalation of cyclopropenes.
Scheme 18: Enantioselective carbozincation of cyclopropenes.
Scheme 19: Copper-catalyzed facially selective carbomagnesiation.
Scheme 20: Arylmagnesiation of cyclopropenes.
Scheme 21: Enantioselective methylmagnesiation of cyclopropenes without catalyst.
Scheme 22: Copper-catalyzed carbozincation.
Scheme 23: Enantioselective ethylzincation of cyclopropenes.
Scheme 24: Nickel-catalyzed ring-opening aryl- and alkenylmagnesiation of a methylenecyclopropane.
Scheme 25: Reaction mechanism.
Scheme 26: Nickel-catalyzed carbomagnesiation of arylacetylene and dialkylacetylene.
Scheme 27: Nickel-catalyzed carbozincation of arylacetylenes and its application to the synthesis of tamoxifen....
Scheme 28: Bristol-Myers Squibb’s nickel-catalyzed phenylzincation.
Scheme 29: Iron/NHC-catalyzed arylmagnesiation of aryl(alkyl)acetylene.
Scheme 30: Iron/copper-cocatalyzed alkylmagnesiation of aryl(alkyl)acetylenes.
Scheme 31: Iron-catalyzed hydrometalation.
Scheme 32: Iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes.
Scheme 33: Chromium-catalyzed arylmagnesiation of alkynes.
Scheme 34: Cobalt-catalyzed arylzincation of alkynes.
Scheme 35: Cobalt-catalyzed formation of arylzinc reagents and subsequent arylzincation of alkynes.
Scheme 36: Cobalt-catalyzed benzylzincation of dialkylacetylene and aryl(alkyl)acetylenes.
Scheme 37: Synthesis of estrogen receptor antagonist.
Scheme 38: Cobalt-catalyzed allylzincation of aryl-substituted alkynes.
Scheme 39: Silver-catalyzed alkylmagnesiation of terminal alkyne.
Scheme 40: Proposed mechanism of silver-catalyzed alkylmagnesiation.
Scheme 41: Zirconium-catalyzed ethylzincation of terminal alkenes.
Scheme 42: Zirconium-catalyzed alkylmagnesiation.
Scheme 43: Titanium-catalyzed carbomagnesiation.
Scheme 44: Three-component coupling reaction.
Scheme 45: Iron-catalyzed arylzincation reaction of oxabicyclic alkenes.
Scheme 46: Reaction of allenyl ketones with organomagnesium reagent.
Scheme 47: Regio- and stereoselective reaction of a 2,3-allenoate.
Scheme 48: Three-component coupling reaction of 1,2-allenoate, organozinc reagent, and ketone.
Scheme 49: Proposed mechanism for a rhodium-catalyzed arylzincation of allenes.
Scheme 50: Synthesis of skipped polyenes by iterative arylzincation/allenylation reaction.
Scheme 51: Synthesis of 1,4-diorganomagnesium compound from 1,2-dienes.
Scheme 52: Synthesis of tricyclic compounds.
Scheme 53: Manganese-catalyzed allylmagnesiation of allenes.
Scheme 54: Copper-catalyzed alkylmagnesiation of 1,3-dienes and 1,3-enynes.
Scheme 55: Chromium-catalyzed methallylmagnesiation of 1,6-diynes.
Scheme 56: Chromium-catalyzed allylmagnesiation of 1,6-enynes.
Scheme 57: Proposed mechanism of the chromium-catalyzed methallylmagnesiation.
Beilstein J. Org. Chem. 2012, 8, 1765–1770, doi:10.3762/bjoc.8.201
Graphical Abstract
Scheme 1: Literature examples of intramolecular TMC [4 + 2] cycloadditions of diene-tethered alkynes.
Scheme 2: Reaction pathways of alkynyl halides in transition-metal-catalyzed reactions.
Scheme 3: Synthesis of diene-tethered alkynyl halides 1c and 1e.
Scheme 4: Synthesis of diene-tethered alkynyl halide 1g.
Scheme 5: Unsuccessful cycloaddition attempts with substrates with a 4-atom tether.
Beilstein J. Org. Chem. 2012, 8, 1246–1255, doi:10.3762/bjoc.8.140
Graphical Abstract
Figure 1: Terpenoids 1–5 present in Alloxysta victrix and cis-fused bicyclic iridoids known from other insect...
Figure 2: 70 eV EI-mass spectrum of the iridoid X, a component of the volatile secretions of the parasitoid w...
Figure 3: Structures and gas chromatographic retention times of trans-fused dihydronepetalactones on a conven...
Scheme 1: Route from (S)-pulegone to the mixture of dihydronepetalactones a and b, consequently following Wol...
Figure 4: Configuration of the dihydronepetalactone a.
Figure 5: Route to stereochemically pure trans-fused dihydronepetalactones a–d from (R)-limonene.
Scheme 2: Synthesis of the key compound 16. Reaction conditions: a) O3, MeOH, −50 °C (86%); b) AcOH, piperidi...
Scheme 3: Synthesis of trans,trans-substituted dihydronepetalactone b. Reaction conditions: a) TBDMSCl, imida...
Figure 6: Configurations of compound 24 and the dihydronepetalactone b.
Scheme 4: Synthesis of cis,trans-substituted dihydronepetalactone c. Reaction conditions: a) Crabtree's catal...
Figure 7: Configurations of compound 26 and the dihydronepetalactone c.
Scheme 5: Synthesis of a 2:3 mixture of dihydronepetalactones c and d. Reaction conditions: a) (COCl)2, DMSO,...
Scheme 6: Formal synthesis of a mixture of dihydronepetalactones a and b from (R)-limonene.
Beilstein J. Org. Chem. 2012, 8, 1200–1207, doi:10.3762/bjoc.8.133
Graphical Abstract
Figure 1: Representative biologically active aminomethylcoumarins.
Scheme 1: Approach to diversely substituted coumarins.
Scheme 2: Scope of the decarboxylative coupling.
Scheme 3: Scope of Suzuki-coupling of coumarinyl acetates.
Scheme 4: Coupling of (coumarinyl)methyl acetates with N- and S-nucleophiles.
Scheme 5: Scope of the coumarinyl acetate and aryl sulfinate coupling reaction.
Scheme 6: Scope of the coumarinyl acetate and amine coupling reaction.
Figure 2: Library planning for amine (A) and coumarin (C) coupling partners.
Figure 3: Results for the synthesis of a 128-member library of aminated coumarins by using the Chemspeed SLT1...
Beilstein J. Org. Chem. 2012, 8, 841–849, doi:10.3762/bjoc.8.94
Graphical Abstract
Figure 1: Structures of Smo antagonists and agonists.
Scheme 1: General synthetic route for Sant-75. Reagents and conditions: (a) Pd(PPh3)4, PhMe, Na2CO3, H2O, 85 ...
Scheme 2: Substituent-modifications on the motif A. Reagents and conditions: (a) CH2Cl2, Et3N; (b) CH2Cl2, TF...
Scheme 3: Substituent-modifications on the motif A. Reagents and conditions: (a) (i) FeCl3, Zn, H2O, DMF, 100...
Scheme 4: Core modification on the motif A. Reagents and conditions: (a) BOP, DIEA, DMF; (b) CH2Cl2, TFA.
Figure 2: Core modification on the motif B.
Scheme 5: Synthesis of key intermediate biaryl aldehydes. Reagents and conditions: (a) Pd(OAc)2, PPh3, 1,4-di...
Scheme 6: Chemical modifications on the motif C. Reagents and conditions: (a) Pd(OAc)2, PPh3, 1,4-dioxane, Na2...
Scheme 7: Chemical modifications on the motif D. Reagents and conditions: (a) R2COCl, CH2Cl2.
Beilstein J. Org. Chem. 2011, 7, 1278–1287, doi:10.3762/bjoc.7.148
Graphical Abstract
Figure 1: Modular synthesis of bis(diarylphosphino)-, bis(dialkylphosphino)- and dialkyl(diaryl)phosphinobiph...
Figure 2: ARYNE coupling.
Scheme 1: Functionalization of 2,2',6-tribromobiphenyl (1a) by regioselective bromine–lithium exchange.
Scheme 2: Functionalization of 2,2'-dibromobiphenyls (1b–e) by regioselective bromine–lithium exchange.
Figure 3: General access to biaryl mono- and diphosphine ligands; (Cy = cyclohexyl).
Scheme 3: Synthesis of monophosphines 3; (Cy = cyclohexyl).
Figure 4: Molecular structure of compound 3a (crystallized from ethyl acetate/hexane) [74].
Scheme 4: Preparation of mixed dialkyl(diaryl)phosphinobiphenyls 5 via successive bromine–lithium exchange.
Scheme 5: Stepwise bromine–lithium exchange on 1c.
Beilstein J. Org. Chem. 2011, 7, 988–996, doi:10.3762/bjoc.7.111
Graphical Abstract
Figure 1: More active GSK HCV inhibitors.
Scheme 1: Retrosynthetic analysis of antiviral structures.
Figure 2: Chiral phosphoramidites tested in this study.
Scheme 2: Optimization of the reaction conditions for the synthesis of the key intermediate 5b.
Scheme 3: Preparation of the enantiomerically enriched 5b.
Scheme 4: Total synthesis of antiviral agent 2b.
Figure 3: Gibbs activation energy and main geometrical features of the computed ylide and transition structur...
Beilstein J. Org. Chem. 2011, 7, 944–950, doi:10.3762/bjoc.7.105
Graphical Abstract
Scheme 1: Cationic gold(I)/PPh3-complex catalyzed intramolecular hydroalkenylation of alkynes.
Scheme 2: Cationic palladium(II)/(S)-xyl-Segphos-complex catalyzed atropselective intramolecular hydroalkenyl...
Scheme 3: Cationic palladium(II)/(S)-xyl-H8-BINAP complex-catalyzed atropselective intramolecular hydroarylat...
Figure 1: Structures of axially chiral biaryl bisphosphine ligands.
Scheme 4: Cationic gold(I)/(R)-DTBM-Segphos-complex catalyzed atropselective intramolecular hydroarylation of...
Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103
Graphical Abstract
Scheme 1: Gold-catalyzed addition of alcohols.
Scheme 2: Gold-catalyzed cycloaddition of alcohols.
Scheme 3: Ionic liquids as the solvent in gold-catalyzed cycloaddition.
Scheme 4: Gold-catalyzed cycloaddition of diynes.
Scheme 5: Gold(I) chloride catalyzed cycloisomerization of 2-alkynyl-1,5-diols.
Scheme 6: Gold-catalyzed cycloaddition of glycols and dihydroxy compounds.
Scheme 7: Gold-catalyzed ring-opening of cyclopropenes.
Scheme 8: Gold-catalyzed intermolecular hydroalkoxylation of alkynes. PR3 = 41–45.
Scheme 9: Gold-catalyzed intramolecular 6-endo-dig cyclization of β-hydroxy-α,α-difluoroynones.
Scheme 10: Gold-catalyzed intermolecular hydroalkoxylation of non-activated olefins.
Scheme 11: Preparation of unsymmetrical ethers from alcohols.
Scheme 12: Expedient synthesis of dihydrofuran-3-ones.
Scheme 13: Catalytic approach to functionalized divinyl ketones.
Scheme 14: Gold-catalyzed glycosylation.
Scheme 15: Gold-catalyzed cycloaddition of aldehydes and ketones.
Scheme 16: Gold-catalyzed annulations of 2-(ynol)aryl aldehydes and o-alkynyl benzaldehydes.
Scheme 17: Gold-catalyzed addition of carboxylates.
Scheme 18: Dual-catalyzed rearrangement reaction of allenoates.
Scheme 19: Meyer–Schuster rearrangement of propargylic alcohols.
Scheme 20: Propargylic alcohol rearrangements.
Scheme 21: Gold-catalyzed synthesis of imines and amine alkylation.
Scheme 22: Hydroamination of allenes and allenamides.
Scheme 23: Gold-catalyzed inter- and intramolecular amination of alkynes and alkenes.
Scheme 24: Gold-catalyzed cycloisomerization of O-propioloyl oximes and β-allenylhydrazones.
Scheme 25: Intra- and intermolecular amination with ureas.
Scheme 26: Gold-catalyzed cyclization of ortho-alkynyl-N-sulfonylanilines and but-3-yn-1-amines.
Scheme 27: Gold-catalyzed piperidine ring synthesis.
Scheme 28: Ring expansion of alkylnyl cyclopropanes.
Scheme 29: Gold-catalyzed annulations of N-propargyl-β-enaminones and azomethine imines.
Scheme 30: Gold(I)-catalyzed cycloisomerization of aziridines.
Scheme 31: AuCl3/AgSbF6-catalyzed intramolecular amination of 2-(tosylamino)phenylprop-1-en-3-ols.
Scheme 32: Gold-catalyzed cyclization via a 7-endo-dig pathway.
Scheme 33: Gold-catalyzed synthesis of fused xanthines.
Scheme 34: Gold-catalyzed synthesis of amides and isoquinolines.
Scheme 35: Gold-catalyzed oxidative cross-coupling reactions of propargylic acetates.
Scheme 36: Gold-catalyzed nucleophilic addition to allenamides.
Scheme 37: Gold-catalyzed direct carbon–carbon bond coupling reactions.
Scheme 38: Gold-catalyzed C−H functionalization of indole/pyrrole heterocycles and non-activated arenes.
Scheme 39: Gold-catalyzed cycloisomerization of cyclic compounds.
Scheme 40: Gold-catalyzed cycloaddition of 1-aryl-1-allen-6-enes and propargyl acetates.
Scheme 41: Gold(I)-catalyzed cycloaddition with ligand-controlled regiochemistry.
Scheme 42: Gold(I)-catalyzed cycloaddition of dienes and enynes.
Scheme 43: Gold-catalyzed intramolecular cycloaddition of 3-alkoxy-1,5-enynes and 2,2-dipropargylmalonates.
Scheme 44: Gold-catalyzed intramolecular cycloaddition of 1,5-allenynes.
Scheme 45: Gold(I)-catalyzed cycloaddition of indoles.
Scheme 46: Gold-catalyzed annulation reactions.
Scheme 47: Gold–carbenoid induced cleavage of a sp3-hybridized C−H bond.
Scheme 48: Furan- and indole-based cascade reactions.
Scheme 49: Tandem process using aromatic alkynes.
Scheme 50: Gold-catalyzed cycloaddition of 1,3-dien-5-ynes.
Scheme 51: Gold-catalyzed cascade cyclization of diynes, propargylic esters, and 1,3-enynyl ketones.
Scheme 52: Tandem reaction of β-phenoxyimino ketones and alkynyl oxime ethers.
Scheme 53: Gold-catalyzed tandem cyclization of enynes, 2-(tosylamino)phenylprop-1-yn-3-ols, and allenoates.
Scheme 54: Cyclization of 2,4-dien-6-yne carboxylic acids.
Scheme 55: Gold(I)-catalyzed tandem cyclization approach to tetracyclic indolines.
Scheme 56: Gold-catalyzed tandem reactions of alkynes.
Scheme 57: Aminoarylation and oxyarylation of alkenes.
Scheme 58: Cycloaddition of 2-ethynylnitrobenzene with various alkenes.
Scheme 59: Gold-catalyzed tandem reactions of allenoates and alkynes.
Scheme 60: Gold-catalyzed asymmetric synthesis of 2,3-dihydropyrroles.
Scheme 61: Chiral [NHC–Au(I)]-catalyzed cyclization of enyne.
Scheme 62: Gold-catalyzed hydroaminations and hydroalkoxylations.
Scheme 63: Gold(I)-catalyzed asymmetric hydroalkoxylation of 1,3-dihydroxymethyl-2-alkynylbenzene chromium com...
Scheme 64: Gold-catalyzed synthesis of julolidine derivatives.
Scheme 65: Gold-catalyzed the synthesis of chiral fused heterocycles.
Scheme 66: Gold-catalyzed asymmetric reactions with 3,5-(t-Bu)2-4-MeO-MeOBIPHEP.
Scheme 67: Gold-catalyzed cyclization of o-(alkynyl) styrenes.
Scheme 68: Asymmetric gold(I)-catalyzed redox-neutral domino reactions of enynes.
Scheme 69: Gold(I)-catalyzed enantioselective polyene cyclization reaction.
Scheme 70: Gold(I)-catalyzed enantioselective synthesis of benzopyrans.
Scheme 71: Gold(I)-catalyzed enantioselective ring expansion of allenylcyclopropanols.
Beilstein J. Org. Chem. 2011, 7, 555–564, doi:10.3762/bjoc.7.64
Graphical Abstract
Figure 1: Monodentate NHCs with sterically hindered N-substituents.
Figure 2: NHCs with axially chiral biaryl frameworks.
Scheme 1: Synthesis of N-heterocyclic carbene precursor.
Scheme 2: Synthesis of mono(NHC)–Pd(II) complex.
Figure 3: ORTEP drawing of NHC–Pd(II) complex (S)-7a with thermal ellipsoids at the 30% probability level. Se...
Scheme 3: Synthesis of mono(NHC)–Au(I) complex.
Figure 4: ORTEP drawing of NHC–Au(I) complex (S)-6a with thermal ellipsoids at the 30% probability level. Sel...
Scheme 4: Synthesis of mono(NHC)–Au(I) complex (S)-6b.
Scheme 5: Synthesis of mono(NHC)–Au(I) complex (S)-6c.
Scheme 6: The application of catalysts (S)-6b and 6c in the intramolecular hydroamination reaction.
Beilstein J. Org. Chem. 2011, 7, 59–74, doi:10.3762/bjoc.7.10
Graphical Abstract
Scheme 1: Synthesis of selective D3 receptor ligands.
Scheme 2: Synthesis of a novel 5-HT1B receptor antagonist.
Scheme 3: Synthesis of A-366833, a selective α4β2 neural nicotinic receptor agonist.
Scheme 4: A new route to oxcarbazepine.
Scheme 5: Synthesis of key intermediates for norepinephrine transporter (NET) inhibitors.
Scheme 6: N-Annulation yielding substituted indole for the synthesis of demethylasterriquinone A1.
Scheme 7: Palladium-catalysed double N-arylation contributing to the synthesis of murrazoline.
Scheme 8: Synthesis of vitamin E amines.
Scheme 9: Improved synthesis of martinellic acid.
Scheme 10: New tariquidar-derived ABCB1 inhibitors.
Scheme 11: β-Carbolin-1-ones as inhibitors of tumour cell proliferation.
Scheme 12: Copper-catalysed synthesis of promazine drugs.
Scheme 13: Palladium-catalysed multicomponent reaction for the synthesis of promazine drugs.
Scheme 14: Key intermediate for imatinib.
Scheme 15: Synthesis of an effective Chek1/KDR kinase inhibitor.
Scheme 16: Macrocyclization as final step of the synthesis of heat shock protein inhibitor.
Scheme 17: Synthesis of N-arylimidazoles.
Scheme 18: Synthesis of benzolactam V8.
Scheme 19: Synthesis of an intermediate for lotrafiban (SB-214857).
Scheme 20: Intermolecular effort towards lotrafiban.
Scheme 21: Synthesis of matrix metalloproteases (MMPs) inhibitor.
Scheme 22: Regioselective 9-N-arylation of purines.
Scheme 23: N-Arylation of adenine and cytosine.
Scheme 24: 9-N-Arylpurines as enterovirus inhibitors.
Scheme 25: Xanthine analogues as kinase inhibitors.
Scheme 26: Synthesis of dual PPARα/γ agonists.
Scheme 27: N-Aryltriazole ribonucleosides with anti-proliferative activity.
Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32
Graphical Abstract
Figure 1: Biologically important amines and quaternary ammonium salts: histamine (1), dopamine (2) and acetyl...
Figure 2: Crown ether 18-crown-6.
Figure 3: Conformations of 18-crown-6 (4) in solvents of different polarity.
Figure 4: Binding topologies of the ammonium ion depending on the crown ring size.
Figure 5: A “pseudorotaxane” structure consisting of 24-crown-8 and a secondary ammonium ion (5); R = Ph.
Figure 6: Typical examples of azacrown ethers, cryptands and related aza macrocycles.
Figure 7: Binding of ammonium to azacrown ethers and cryptands [111-113].
Figure 8: A 19-crown-6-ether with decalino blocking groups (11) and a thiazole-dibenzo-18-crown-6-ether (12).
Figure 9: 1,3-Bis(6-oxopyridazin-1-yl)propane derivatives 13 and 14 by Campayo et al.
Figure 10: Fluorescent azacrown-PET-sensors based on coumarin.
Figure 11: Two different pyridino-cryptands (17 and 18) compared to a pyridino-crown (19); chiral ammonium ion...
Figure 12: Pyridino-18-crown-6 ligand (21), a similar acridino-18-crown-6 ligand (22) and a structurally relat...
Figure 13: Ciral pyridine-azacrown ether receptors 24.
Figure 14: Chiral 15-crown-5 receptors 26 and an analogue 18-crown-6 ligand 27 derived from amino alcohols.
Figure 15: C2-symmetric chiral 18-crown-6 amino alcohol derivatives 28 and related macrocycles.
Figure 16: Macrocycles with diamide-diester groups (30).
Figure 17: C2-symmetric chiral aza-18-crown-6 ethers (31) with phenethylamine residues.
Figure 18: Chiral C-pivot p-methoxy-phenoxy-lariat ethers.
Figure 19: Chiral lariat crown ether 34.
Figure 20: Sucrose-based chiral crown ether receptors 36.
Figure 21: Permethylated fructooligosaccharide 37 showing induced-fit chiral recognition.
Figure 22: Biphenanthryl-18-crown-6 derivative 38.
Figure 23: Chiral lariat crown ethers derived from binol by Fuji et al.
Figure 24: Chiral phenolic crown ether 41 with “aryl chiral barriers” and guest amines.
Figure 25: Chiral bis-crown receptor 43 with a meso-ternaphthalene backbone.
Figure 26: Chromogenic pH-dependent bis-crown chemosensor 44 for diamines.
Figure 27: Triamine guests for binding to receptor 44.
Figure 28: Chiral bis-crown phenolphthalein chemosensors 46.
Figure 29: Crown ether amino acid 47.
Figure 30: Luminescent receptor 48 for bis-alkylammonium guests.
Figure 31: Luminescent CEAA (49a), a bis-CEAA receptor for amino acids (49b) and the structure of lysine bindi...
Figure 32: Luminescent CEAA tripeptide for binding small peptides.
Figure 33: Bis crown ether 51a self assembles co-operatively with C60-ammonium ion 51b.
Figure 34: Triptycene-based macrotricyclic dibenzo-[24]-crown-8 ether host 52 and guests.
Figure 35: Copper imido diacetic acid azacrown receptor 53a and the suggested His-Lys binding motif; a copper ...
Figure 36: Urea (54) and thiourea (55) benzo crown receptor for transport and extraction of amino acids.
Figure 37: Crown pyryliums ion receptors 56 for amino acids.
Figure 38: Ditopic sulfonamide bridged crown ether receptor 57.
Figure 39: Luminescent peptide receptor 58.
Figure 40: Luminescent receptor 59 for the detection of D-glucosamine hydrochloride in water/ethanol and lumin...
Figure 41: Guanidinium azacrown receptor 61 for simple amino acids and ditopic receptor 62 with crown ether an...
Figure 42: Chiral bicyclic guanidinium azacrown receptor 63 and similar receptor 64 for the enantioselective t...
Figure 43: Receptors for zwitterionic species based on luminescent CEAAs.
Figure 44: 1,10-Azacrown ethers with sugar podand arms and the anticancer agent busulfan.
Figure 45: Benzo-18-crown-6 modified β-cyclodextrin 69 and β-cyclodextrin functionalized with diaza-18-crown-6...
Figure 46: Receptors for colorimetric detection of primary and secondary ammonium ions.
Figure 47: Porphyrine-crown-receptors 72.
Figure 48: Porphyrin-crown ether conjugate 73 and fullerene-ammonium ion guest 74.
Figure 49: Calix[4]arene (75a), homooxocalix[4]arene (75b) and resorcin[4]arene (75c) compared (R = H, alkyl c...
Figure 50: Calix[4]arene and ammonium ion guest (R = H, alkyl, OAcyl etc.), possible binding sites; A: co-ordi...
Figure 51: Typical guests for studies with calixarenes and related molecules.
Figure 52: Lower rim modified p-tert-butylcalix[5]arenes 82.
Figure 53: The first example of a water soluble calixarene.
Figure 54: Sulfonated water soluble calix[n]arenes that bind ammonium ions.
Figure 55: Displacement assay for acetylcholine (3) with a sulfonato-calix[6]arene (84b).
Figure 56: Amino acid inclusion in p-sulfonatocalix[4]arene (84a).
Figure 57: Calixarene receptor family 86 with upper and lower rim functionalization.
Figure 58: Calix[6]arenes 87 with one carboxylic acid functionality.
Figure 59: Sulfonated calix[n]arenes with mono-substitution at the lower rim systematically studied on their r...
Figure 60: Cyclotetrachromotropylene host (91) and its binding to lysine (81c).
Figure 61: Calixarenes 92 and 93 with phosphonic acids groups.
Figure 62: Calix[4]arene tetraphosphonic acid (94a) and a double bridged analogue (94b).
Figure 63: Calix[4]arene tetraphosphonic acid ester (92c) for surface recognition experiments.
Figure 64: Calixarene receptors 95 with α-aminophosphonate groups.
Figure 65: A bridged homocalix[3]arene 95 and a distally bridged homocalix[4]crown 96.
Figure 66: Homocalix[3]arene ammonium ion receptor 97a and the Reichardt’s dye (97b) for colorimetric assays.
Figure 67: Chromogenic diazo-bridged calix[4]arene 98.
Figure 68: Calixarene receptor 99 by Huang et al.
Figure 69: Calixarenes 100 reported by Parisi et al.
Figure 70: Guest molecules for inclusion in calixarenes 100: DAP × 2 HCl (101a), APA (101b) and Lys-OMe × 2 HC...
Figure 71: Different N-linked peptido-calixarenes open and with glycol chain bridges.
Figure 72: (S)-1,1′-Bi-2-naphthol calixarene derivative 104 published by Kubo et al.
Figure 73: A chiral ammonium-ion receptor 105 based on the calix[4]arene skeleton.
Figure 74: R-/S-phenylalaninol functionalized calix[6]arenes 106a and 106b.
Figure 75: Capped homocalix[3]arene ammonium ion receptor 107.
Figure 76: Two C3 symmetric capped calix[6]arenes 108 and 109.
Figure 77: Phosphorous-containing rigidified calix[6]arene 110.
Figure 78: Calix[6]azacryptand 111.
Figure 79: Further substituted calix[6]azacryptands 112.
Figure 80: Resorcin[4]arene (75c) and the cavitands (113).
Figure 81: Tetrasulfonatomethylcalix[4]resorcinarene (114).
Figure 82: Resorcin[4]arenes (115a/b) and pyrogallo[4]arenes (115c, 116).
Figure 83: Displacement assay for acetylcholine (3) with tetracyanoresorcin[4]arene (117).
Figure 84: Tetramethoxy resorcinarene mono-crown-5 (118).
Figure 85: Components of a resorcinarene based displacement assay for ammonium ions.
Figure 86: Chiral basket resorcin[4]arenas 121.
Figure 87: Resorcinarenes with deeper cavitand structure (122).
Figure 88: Resorcinarene with partially open deeper cavitand structure (123).
Figure 89: Water-stabilized deep cavitands with partially structure (124, 125).
Figure 90: Charged cavitands 126 for tetralkylammonium ions.
Figure 91: Ditopic calix[4]arene receptor 127 capped with glycol chains.
Figure 92: A calix[5]arene dimer for diammonium salt recognition.
Figure 93: Calixarene parts 92c and 129 for the formation molecular capsules.
Figure 94: Encapsulation of a quaternary ammonium cation by two resorcin[4]arene molecules (NMe4+@[75c]2 × Cl−...
Figure 95: Encapsulation of a quaternary ammonium cation by six resorcin[4]arene molecules (NMe3D+@[130]6 × Cl−...
Figure 96: Structure and schematic of cucurbit[6]uril (CB[6], 131a).
Figure 97: Cyclohexanocucurbit[6]uril (CB′[6], 132) and the guest molecule spermine (133).
Figure 98: α,α,δ,δ-Tetramethylcucurbit[6]uril (134).
Figure 99: Structure of the cucurbituril-phthalhydrazide analogue 135.
Figure 100: Organic cavities for the displacement assay for amine differentiation.
Figure 101: Displacement assay methodology for diammonium- and related guests involving cucurbiturils and some ...
Figure 102: Nor-seco-Cucurbituril (±)-bis-ns-CB[6] (140) and guest molecules.
Figure 103: The cucurbit[6]uril based complexes 141 for chiral discrimination.
Figure 104: Cucurbit[7]uril (131c) and its ferrocene guests (142) opposed.
Figure 105: Cucurbit[7]uril (131c) guest inclusion and representative guests.
Figure 106: Cucurbit[7]uril (131c) binding to succinylcholine (145) and different bis-ammonium and bis-phosphon...
Figure 107: Paraquat-cucurbit[8]uril complex 149.
Figure 108: Gluconuril-based ammonium receptors 150.
Figure 109: Examples of clefts (151a), tweezers (151b, 151c, 151d) and clips (151e).
Figure 110: Kemp’s triacid (152a), on example of Rebek’s receptors (152b) and guests.
Figure 111: Amino acid receptor (154) by Rebek et al.
Figure 112: Hexagonal lattice designed hosts by Bell et al.
Figure 113: Bell’s amidinium receptor (156) and the amidinium ion (157).
Figure 114: Aromatic phosphonic acids.
Figure 115: Xylene phosphonates 159 and 160a/b for recognition of amines and amino alcohols.
Figure 116: Bisphosphonate recognition motif 161 for a colorimetric assay with alizarin complexone (163) for ca...
Figure 117: Bisphosphonate/phosphate clip 164 and bisphosphonate cleft 165.
Figure 118: N-Methylpyrazine 166a, N-methylnicotinamide iodide (166b) and NAD+ (166c).
Figure 119: Bisphosphate cavitands.
Figure 120: Bisphosphonate 167 of Schrader and Finocchiaro.
Figure 121: Tweezer 168 for noradrenaline (80b).
Figure 122: Different tripods and heparin (170).
Figure 123: Squaramide based receptors 172.
Figure 124: Cage like NH4+ receptor 173 of Kim et al.
Figure 125: Ammonium receptors 174 of Chin et al.
Figure 126: 2-Oxazolin-based ammonium receptors 175a–d and 176 by Ahn et al.
Figure 127: Racemic guest molecules 177.
Figure 128: Tripods based on a imidazole containing macrocycle (178) and the guest molecules employed in the st...
Figure 129: Ammonium ion receptor 180.
Figure 130: Tetraoxa[3.3.3.3]paracyclophanes 181 and a cyclophanic tetraester (182).
Figure 131: Peptidic bridged paraquat-cyclophane.
Figure 132: Shape-selective noradrenaline host.
Figure 133: Receptor 185 for binding of noradrenaline on surface layers from Schrader et al.
Figure 134: Tetraphosphonate receptor for binding of noradrenaline.
Figure 135: Tetraphosphonate 187 of Schrader and Finocchiaro.
Figure 136: Zinc-Porphyrin ammonium-ion receptors 188 and 189 of Mizutani et al.
Figure 137: Zinc porphyrin receptor 190.
Figure 138: Zinc porphyrin receptors 191 capable of amino acid binding.
Figure 139: Zinc-porphyrins with amino acid side chains for stereoinduction.
Figure 140: Bis-zinc-bis-porphyrin based on Tröger’s base 193.
Figure 141: BINAP-zinc-prophyrin derivative 194 and it’s guests.
Figure 142: Bisaryl-linked-zinc-porphyrin receptors.
Figure 143: Bis-zinc-porphyrin 199 for diamine recognition and guests.
Figure 144: Bis-zinc-porphyrin crown ether 201.
Figure 145: Bis-zinc-porphyrin 202 for stereodiscrimination (L = large substituent; S = small substituent).
Figure 146: Bis-zinc-porphyrin[3]rotaxane and its copper complex and guests.
Figure 147: Dien-bipyridyl ligand 206 for co-ordination of two metal atoms.
Figure 148: The ligand and corresponding tetradentate co-complex 207 serving as enantioselective receptor for a...
Figure 149: Bis(oxazoline)–copper(II) complex 208 for the recognition of amino acids in aqueous solution.
Figure 150: Zinc-salen-complexes 209 for the recognition tertiary amines.
Figure 151: Bis(oxazoline)–copper(II) 211 for the recognition of amino acids in aqueous solution.
Figure 152: Zn(II)-complex of a C2 terpyridine crown ether.
Figure 153: Displacement assay and receptor for aspartate over glutamate.
Figure 154: Chiral complex 214 for a colorimetric displacement assay for amino acids.
Figure 155: Metal complex receptor 215 with tripeptide side arms.
Figure 156: A sandwich complex 216 and its displaceable dye 217.
Figure 157: Lanthanide complexes 218–220 for amino acid recognition.
Figure 158: Nonactin (221), valinomycin (222) and vancomycin (223).
Figure 159: Monesin (224a) and a chiral analogue for enantiodiscrimination of ammonium guests (224b).
Figure 160: Chiral podands (226) compared to pentaglyme-dimethylether (225) and 18-crown-6 (4).
Figure 161: Lasalocid A (228).
Figure 162: Lasalocid derivatives (230) of Sessler et al.
Figure 163: The Coporphyrin I tetraanion (231).
Figure 164: Linear and cyclic peptides for ammonium ion recognition.
Figure 165: Cyclic and bicyclic depsipeptides for ammonium ion recognition.
Figure 166: α-Cyclodextrin (136a) and novocaine (236).
Figure 167: Helical diol receptor 237 by Reetz and Sostmann.
Figure 168: Ammonium binding spherand by Cram et al. (238a) and the cyclic[6]metaphenylacetylene 238b in compar...
Figure 169: Receptor for peptide backbone and ammonium binding (239).
Figure 170: Anion sensor principle with 3-hydroxy-2-naphthanilide of Jiang et al.
Figure 171: 7-bromo-3-hydroxy-N-(2-hydroxyphenyl)naphthalene 2-carboxamide (241) and its amine binding.
Figure 172: Naturally occurring catechins with affinity to quaternary ammonium ions.
Figure 173: Spiropyran (244) and merocyanine form (244a) of the amino acid receptors of Fuji et al.
Figure 174: Coumarin aldehyde (245) and its iminium species with amino acid bound (245a) by Glass et al.
Figure 175: Coumarin aldehyde appended with boronic acid.
Figure 176: Quinolone aldehyde dimers by Glass et al.
Figure 177: Chromogenic ammonium ion receptors with trifluoroacetophenone recognition motifs.
Figure 178: Chromogenic ammonium ion receptor with trifluoroacetophenone recognition motif bound on different m...
Beilstein J. Org. Chem. 2009, 5, No. 53, doi:10.3762/bjoc.5.53
Graphical Abstract
Scheme 1: Identification of optimal chiral ligand for iridium-catalyzed asymmetric ring-opening of oxabenzono...
Figure 1: ORTEP plot for 3f.
Scheme 2: Proposed mechanism for the ARO of oxabenzonorbornadiene 1a with secondary amine nucleophiles.
Beilstein J. Org. Chem. 2008, 4, No. 16, doi:10.3762/bjoc.4.16
Graphical Abstract
Figure 1: Structures of DBFOX-Ph, Box-Ph and NFSI.
Scheme 1: Transition-State Structure for the DBFOX-Ph/Ni(II) Catalyzed Enantioselective Fluorination of 1 to 2...
Beilstein J. Org. Chem. 2007, 3, No. 5, doi:10.1186/1860-5397-3-5
Graphical Abstract
Scheme 1: Retrosynthetic analysis for the homopterocarpan skeleton.
Scheme 2: Reagents: i CH2 = CHCH2SiMe2Cl, Et3N, DCM, 85%; ii 2nd generation Grubbs catalyst, DCM, 91%.
Scheme 3: Reagents: i: BF3·Et2O (1 eq), MeOH 95%; ii: substituted benzaldehydes, BF3·Et2O (1 eq), DCM; iii: s...
Scheme 4: Reagents: i: a) OsO4, KIO4, THF-H2O, 79%; b) LiAlH4, Et2, 0°C, 76%; iii: PPh3, DIAD, THF, 70%.
Beilstein J. Org. Chem. 2006, 2, No. 18, doi:10.1186/1860-5397-2-18
Graphical Abstract
Scheme 1: Asymmetric aza-Diels-Alder reaction of Danishefsky's diene 1 with imines 2.
Figure 1: Possible interactions of substrates or intermediate of the aza-Diels-Alder reaction with the chiral...