Search for "configurational stability" in Full Text gives 19 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51
Graphical Abstract
Scheme 1: Representative transition-metal catalysis for allylic substitution.
Scheme 2: Formation of stereogenic centers in copper-catalyzed allylic alkylation reactions.
Scheme 3: Copper-mediated, stereospecific SN2-selective allylic substitution through retentive transmetalatio...
Scheme 4: ZnCl2-promoted stereospecific SN2' allylic substitution of secondary alkylcopper species via sequen...
Scheme 5: Temperature and time-dependent configurational stability of chiral secondary organocopper species.
Scheme 6: DFT analysis of B–C bond lengths in various boronate complexes and correlation with reactivity.
Scheme 7: Copper-catalyzed stereospecific allylic alkylation of secondary alkylboronic esters via tert-butyll...
Scheme 8: Copper-catalyzed stereospecific allylic alkylation of chiral tertiary alkylboronic esters via adama...
Scheme 9: DFT-calculated energy surface for boron-to-copper transmetalation of either the tert-butyl group or...
Scheme 10: CuH-catalyzed enantioselective allylic substitution and postulated catalytic cycle.
Scheme 11: CuH-catalyzed enantioselective allylic substitution of vinylarenes.
Scheme 12: CuH-catalyzed stereoselective allylic substitution of vinylboronic esters.
Scheme 13: (a) Generation of chiral copper species via enantioselective CuH addition to vinylBpin. (b) Regardi...
Scheme 14: CuH-catalyzed enantioselective allylic substitution of 1‐trifluoromethylalkenes with 18-crown-6.
Scheme 15: CuH-catalyzed enantioselective allylic substitution of terminal alkynes.
Scheme 16: Copper-catalyzed enantiotopic-group-selective allylic substitution of 1,1-diborylalkanes.
Scheme 17: (a) Computational and (b) experimental studies to elucidate the mechanistic details of the enantiot...
Scheme 18: Copper-catalyzed regio-, diastereo- and enantioselective allylic substitution of 1,1-diborylalkanes....
Scheme 19: (a) Experimental and (b) computational studies to understand the stereoselectivities in oxidative a...
Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6
Graphical Abstract
Scheme 1: Formation of axially chiral styrenes 3 via iminium activation.
Scheme 2: Synthesis of axially chiral 2-arylquinolines 6.
Scheme 3: Atroposelective intramolecular (4 + 2) annulation leading to aryl-substituted indolines.
Scheme 4: Atroposelective formation of biaryl via twofold aldol condensation.
Scheme 5: Strategy towards diastereodivergent formation of axially chiral oligonaphthylenes.
Scheme 6: Atroposelective formation of chiral biaryls based on a Michael/Henry domino reaction.
Scheme 7: Organocatalytic Michael/aldol cascade followed by oxidative aromatization.
Scheme 8: Atroposelective formation of C(sp2)–C(sp3) axially chiral compounds.
Scheme 9: NHC-catalyzed synthesis of axially chiral styrenes 26.
Scheme 10: NHC-catalyzed synthesis of biaxial chiral pyranones.
Scheme 11: Formation of bridged biaryls with eight-membered lactones.
Scheme 12: The NHC-catalyzed (3 + 2) annulation of urazoles 37 and ynals 36.
Scheme 13: NHC-catalyzed synthesis of axially chiral 4‑aryl α‑carbolines 41.
Scheme 14: NHC-catalyzed construction of N–N-axially chiral pyrroles and indoles.
Scheme 15: NHC-catalyzed oxidative Michael–aldol cascade.
Scheme 16: NHC-catalyzed (4 + 2) annulation for the synthesis of benzothiophene-fused biaryls.
Scheme 17: NHC-catalyzed desymmetrization of N-aryl maleimides.
Scheme 18: NHC-catalyzed deracemization of biaryl hydroxy aldehydes 55a–k into axially chiral benzonitriles 56a...
Scheme 19: NHC-catalyzed desymmetrization of 2-aryloxyisophthalaldehydes.
Scheme 20: NHC-catalyzed DKR of 2-arylbenzaldehydes 62.
Scheme 21: Atroposelective biaryl amination.
Scheme 22: CPA-catalyzed atroposelective amination of 2-anilinonaphthalenes.
Scheme 23: Atroposelective DKR of naphthylindoles.
Scheme 24: CPA-catalyzed kinetic resolution of binaphthylamines.
Scheme 25: Atroposelective amination of aromatic amines with diazodicarboxylates.
Scheme 26: Atroposelective Friedländer heteroannulation.
Scheme 27: CPA-catalyzed formation of axially chiral 4-arylquinolines.
Scheme 28: CPA-catalyzed Friedländer reaction of arylketones with cyclohexanones.
Scheme 29: CPA-catalyzed atroposelective Povarov reaction.
Scheme 30: Atroposelective CPA-catalyzed Povarov reaction.
Scheme 31: Paal–Knorr formation of axially chiral N-pyrrolylindoles and N-pyrrolylpyrroles.
Scheme 32: Atroposelective Paal–Knorr reaction leading to N-pyrrolylpyrroles.
Scheme 33: Atroposelective Pictet–Spengler reaction of N-arylindoles with aldehydes.
Scheme 34: Atroposelective Pictet–Spengler reaction leading to tetrahydroisoquinolin-8-ylanilines.
Scheme 35: Atroposelective formation of arylindoles.
Scheme 36: CPA-catalyzed arylation of naphthoquinones with indolizines.
Scheme 37: Atroposelective reaction of o-naphthoquinones.
Scheme 38: CPA-catalyzed formation of axially chiral arylquinones.
Scheme 39: CPA-catalyzed axially chiral N-arylquinones.
Scheme 40: Atroposelective additions of bisindoles to isatin-based 3-indolylmethanols.
Scheme 41: CPA-catalyzed synthesis of axially chiral arylindolylindolinones.
Scheme 42: CPA-catalyzed reaction between bisindoles and ninhydrin-derived 3-indoylmethanols.
Scheme 43: Atroposelective reaction of bisindoles and isatin-derived imines.
Scheme 44: CPA-catalyzed formation of axially chiral bisindoles.
Scheme 45: Atroposelective reaction of 2-naphthols with alkynylhydroxyisoindolinones.
Scheme 46: CPA-catalyzed reaction of indolylnaphthols with propargylic alcohols.
Scheme 47: Atroposelective formation of indolylpyrroloindoles.
Scheme 48: Atroposelective reaction of indolylnaphthalenes with alkynylnaphthols.
Scheme 49: CPA-catalyzed addition of naphthols to alkynyl-2-naphthols and 2-naphthylamines.
Scheme 50: CPA-catalyzed formation of axially chiral aryl-alkene-indoles.
Scheme 51: CPA-catalyzed formation of axially chiral styrenes.
Scheme 52: Atroposelective formation of alkenylindoles.
Scheme 53: Atroposelective formation of axially chiral arylquinolines.
Scheme 54: Atroposelective (3 + 2) cycloaddition of alkynylindoles with azonaphthalenes.
Scheme 55: CPA-catalyzed formation of axially chiral 3-(1H-benzo[d]imidazol-2-yl)quinolines.
Scheme 56: Atroposelective cyclization of 3-(arylethynyl)-1H-indoles.
Scheme 57: Atroposelective three-component heteroannulation.
Scheme 58: CPA-catalyzed formation of arylbenzimidazols.
Scheme 59: CPA-catalyzed reaction of N-naphthylglycine esters with nitrosobenzenes.
Scheme 60: CPA-catalyzed formation of axially chiral N-arylbenzimidazoles.
Scheme 61: CPA-catalyzed formation of axially chiral arylbenzoindoles.
Scheme 62: CPA-catalyzed formation of pyrrolylnaphthalenes.
Scheme 63: CPA-catalyzed addition of naphthols and indoles to nitronaphthalenes.
Scheme 64: Atroposelective reaction of heterobiaryl aldehydes and aminobenzamides.
Scheme 65: Atroposelective cyclization forming N-arylquinolones.
Scheme 66: Atroposelective formation of 9H-carbazol-9-ylnaphthalenes and 1H-indol-1-ylnaphthalene.
Scheme 67: CPA-catalyzed formation of pyrazolylnaphthalenes.
Scheme 68: Atroposelective addition of diazodicarboxamides to azaborinephenols.
Scheme 69: Catalytic formation of axially chiral arylpyrroles.
Scheme 70: Atroposelective coupling of 1-azonaphthalenes with 2-naphthols.
Scheme 71: CPA-catalyzed formation of axially chiral oxindole-based styrenes.
Scheme 72: Atroposelective electrophilic bromination of aminonaphthoquinones.
Scheme 73: Atroposelective bromination of dienes.
Scheme 74: CPA-catalyzed formation of axially chiral 5-arylpyrimidines.
Scheme 75: Atroposelective hydrolysis of biaryloxazepines.
Scheme 76: Atroposelective opening of dinaphthosiloles.
Scheme 77: Atroposelective reduction of naphthylenals.
Scheme 78: Atroposelective allylic substitution with 2-naphthols.
Scheme 79: Atroposelective allylic alkylation with phosphinamides.
Scheme 80: Atroposelective allylic substitution with aminopyrroles.
Scheme 81: Atroposelective allylic substitution with aromatic sulfinamides.
Scheme 82: Atroposelective sulfonylation of naphthylynones.
Scheme 83: Squaramide-catalyzed reaction of alkynyl-2-naphthols with 5H-oxazolones.
Scheme 84: Formation of axially chiral styrenes via sulfonylative opening of cyclopropanols.
Scheme 85: Atroposelective organo-photocatalyzed sulfonylation of alkynyl-2-naphthols.
Scheme 86: Thiourea-catalyzed atroposelective cyclization of alkynylnaphthols.
Scheme 87: Squaramide-catalyzed formation of axially chiral naphthylisothiazoles.
Scheme 88: Atroposelective iodo-cyclization catalyzed by squaramide C69.
Scheme 89: Squaramide-catalyzed formation of axially chiral oligoarenes.
Scheme 90: Atroposelective ring-opening of cyclic N-sulfonylamides.
Scheme 91: Thiourea-catalyzed kinetic resolution of naphthylpyrroles.
Scheme 92: Atroposelective ring-opening of arylindole lactams.
Scheme 93: Atroposelective reaction of 1-naphthyl-2-tetralones and diarylphosphine oxides.
Scheme 94: Atroposelective reaction of iminoquinones with indoles.
Scheme 95: Kinetic resolution of binaphthylalcohols.
Scheme 96: DKR of hydroxynaphthylamides.
Scheme 97: Atroposelective N-alkylation with phase-transfer catalyst C75.
Scheme 98: Atroposelective allylic substitution via kinetic resolution of biarylsulfonamides.
Scheme 99: Atroposelective bromo-functionalization of alkynylarenes.
Scheme 100: Sulfenylation-induced atroposelective cyclization.
Scheme 101: Atroposelective O-sulfonylation of isochromenone-indoles.
Scheme 102: NHC-catalyzed atroposelective N-acylation of anilines.
Scheme 103: Peptide-catalyzed atroposelective ring-opening of lactones.
Scheme 104: Peptide-catalyzed coupling of 2-naphthols with quinones.
Scheme 105: Atroposelective nucleophilic aromatic substitution of fluoroarenes.
Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53
Graphical Abstract
Figure 1: Molecular structures of (R)-BINOL (left) and (S)-BINOL (right).
Figure 2: Synthesis of Sauvage´s [2]catenanes (S,S)-5 and (S,S)-6 containing two BINOL units by the passive m...
Figure 3: Synthesis of Saito´s [2]rotaxane (R)-10 from a BINOL-based macrocycle by the active metal template ...
Figure 4: Synthesis of Stoddart´s [2]rotaxane (rac)-14 by an ammonium crown ether template.
Figure 5: Synthesis of Stoddart´s BINOL-containing [2]catenanes 18/20/22/24 by π–π recognition.
Figure 6: Synthesis of Takata´s rotaxanes featuring chiral centers on the axle: a) rotaxane (R,R,R/S)-27 obta...
Figure 7: Takata´s chiral polyacetylenes 32/33 featuring BINOL-based [2]rotaxane side chains.
Figure 8: Synthesis of Takata´s chiral thiazolium [2]rotaxanes (R)-35a/b and (R)-38.
Figure 9: Results for the asymmetric benzoin condensation of benzaldehyde (39) with catalysts (R)-35a/b and (R...
Figure 10: Synthesis of Takata´s pyridine-based [2]rotaxane (R)-42.
Figure 11: The asymmetric desymmetrization reaction of meso-1,2-diols with rotaxane (R)-42.
Figure 12: Synthesis of Niemeyer´s axially chiral [2]catenane (S,S)-47.
Figure 13: Results for the enantioselective transfer hydrogenation of 2-phenylquinoline with catalysts (S,S)-47...
Figure 14: Synthesis of Niemeyer´s chiral [2]rotaxanes (S)-56/57.
Figure 15: Results for the enantioselective Michael addition with different rotaxane catalysts (S)-56a/56b/57a/...
Figure 16: Synthesis of Beer´s [2]rotaxanes 64a/b for anion recognition.
Figure 17: Association constants of different anions (used as the Bu4N+ salts) to the [2]rotaxanes (S)-64a/b a...
Figure 18: Synthesis of Beer´s [3]rotaxane (S)-68.
Figure 19: Association constants of different anions (used as the Bu4N+-salts) to the [2]rotaxane (S)-68 and a...
Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185
Graphical Abstract
Figure 1: Representative examples of axially chiral biaryls, heterobiaryls, spiranes and allenes as ligands a...
Figure 2: Selected examples of axially chiral drugs and bioactive molecules.
Figure 3: Axially chiral functional materials and supramolecules.
Figure 4: Important chiral phosphoric acid scaffolds used in this review.
Scheme 1: Atroposelective aryl–aryl-bond formation by employing a facile [3,3]-sigmatropic rearrangement.
Scheme 2: Atroposelective synthesis of axially chiral biaryl amino alcohols 5.
Scheme 3: The enantioselective reaction of quinone and 2-naphthol derivatives.
Scheme 4: Enantioselective synthesis of multisubstituted biaryls.
Scheme 5: Enantioselective synthesis of axially chiral quinoline-derived biaryl atropisomers mediated by chir...
Scheme 6: Pd-Catalyzed atroposelective C–H olefination of biarylamines.
Scheme 7: Palladium-catalyzed directed atroposelective C–H allylation.
Scheme 8: Enantioselective synthesis of axially chiral (a) aryl indoles and (b) biaryldiols.
Scheme 9: Asymmetric arylation of indoles enabled by azo groups.
Scheme 10: Proposed mechanism for the asymmetric arylation of indoles.
Scheme 11: Enantioselective synthesis of axially chiral N-arylindoles [38].
Scheme 12: Enantioselective [3 + 2] formal cycloaddition and central-to-axial chirality conversion.
Scheme 13: Organocatalytic atroposelective arene functionalization of nitrosonaphthalene with indoles.
Scheme 14: Proposed reaction mechanism for the atroposelective arene functionalization of nitrosonaphthalenes.
Scheme 15: Asymmetric construction of axially chiral naphthylindoles [65].
Scheme 16: Enantioselective synthesis of axially chiral 3,3’-bisindoles [66].
Scheme 17: Atroposelective synthesis of 3,3’-bisiindoles bearing axial and central chirality.
Scheme 18: Enantioselective synthesis of axially chiral 3,3’-bisindoles bearing single axial chirality.
Scheme 19: Enantioselective reaction of azonaphthalenes with various pyrazolones.
Scheme 20: Enantioselective and atroposelective synthesis of axially chiral N-arylcarbazoles [73].
Scheme 21: Atroposelective cyclodehydration reaction.
Scheme 22: Atroposelective construction of axially chiral N-arylbenzimidazoles [78].
Scheme 23: Proposed reaction mechanism for the atroposelective synthesis of axially chiral N-arylbenzimidazole...
Scheme 24: Atroposelective synthesis of axially chiral arylpyrroles [21].
Scheme 25: Synthesis of axially chiral arylquinazolinones and its reaction pathway [35].
Scheme 26: Synthesis of axially chiral aryquinoline by Friedländer heteroannulation reaction and its proposed...
Scheme 27: Povarov cycloaddition–oxidative chirality conversion process.
Scheme 28: Atroposelective synthesis of oxindole-based axially chiral styrenes via kinetic resolution.
Scheme 29: Synthesis of axially chiral alkene-indole frame works [45].
Scheme 30: Proposed reaction mechanism for axially chiral alkene-indoles.
Scheme 31: Atroposelective C–H aminations of N-aryl-2-naphthylamines with azodicarboxylates.
Scheme 32: Synthesis of brominated atropisomeric N-arylquinoids.
Scheme 33: The enantioselective syntheses of axially chiral SPINOL derivatives.
Scheme 34: γ-Addition reaction of various 2,3-disubstituted indoles to β,γ-alkynyl-α-imino esters.
Scheme 35: Regio- and stereoselective γ-addition reactions of isoxazol-5(4H)-ones to β,γ-alkynyl-α-imino ester...
Scheme 36: Synthesis of chiral tetrasubstituted allenes and naphthopyrans.
Scheme 37: Asymmetric remote 1,8-conjugate additions of thiazolones and azlactones to propargyl alcohols.
Scheme 38: Synthesis of chiral allenes from 1-substituted 2-naphthols [107].
Beilstein J. Org. Chem. 2020, 16, 895–903, doi:10.3762/bjoc.16.81
Graphical Abstract
Scheme 1: The previously reported family of the boomerang bipyrroles obtained by Pd-induced double C–H bond a...
Scheme 2: Synthesis and structures of α-free and α-oxygenated bipyrrole boomerangs. Reagents and conditions: ...
Figure 1: DFT-Optimized structures (B3LYP/6-31G(d,p)) of cNDA2O and cNMI3H.
Figure 2: Absorption and emission spectra of cNMI2H (top) and cNMI3H (bottom) measured in toluene, dichlorome...
Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35
Graphical Abstract
Scheme 1: Synthesis of pyridylphosphine ligands.
Figure 1: Pyridylphosphine ligands.
Scheme 2: Synthesis of piperidyl- and oxazinylphosphine ligands.
Scheme 3: Synthesis of linear multi-chelate pyridylphosphine ligands.
Scheme 4: Synthesis of chiral acetal pyridylphosphine ligands.
Scheme 5: Synthesis of diphenylphosphine-substituted triazine ligands.
Scheme 6: Synthesis of (pyridine-2-ylmethyl)phosphine ligands.
Scheme 7: Synthesis of diphosphine pyrrole ligands.
Scheme 8: Synthesis of 4,5-diazafluorenylphosphine ligands.
Scheme 9: Synthesis of thioether-containing pyridyldiphosphine ligands starting from ethylene sulfide and dip...
Scheme 10: Synthesis of monoterpene-derived phosphine pyridine ligands.
Scheme 11: Synthesis of N-phenylphosphine-substituted imidazole ligands.
Scheme 12: Synthesis of triazol-4-ylphosphine ligands.
Scheme 13: Synthesis of phosphanyltriazolopyridines and product selectivity depending on the substituents’ eff...
Scheme 14: Synthesis of PTA-phosphine ligands.
Scheme 15: Synthesis of isomeric phosphine dipyrazole ligands by varying the reaction temperature.
Scheme 16: Synthesis of N-tethered phosphine imidazolium ligands (route A) and diphosphine imidazolium ligands...
Scheme 17: Synthesis of {1-[2-(pyridin-2-yl)- (R = CH) and {1-[2-(pyrazin-2-yl)quinazolin-4-yl]naphthalen-2-yl...
Scheme 18: Synthesis of oxazolylindolylphosphine ligands 102.
Scheme 19: Synthesis of pyrrolylphosphine ligands.
Scheme 20: Synthesis of phosphine guanidinium ligands.
Scheme 21: Synthesis of a polydentate aminophosphine ligand.
Scheme 22: Synthesis of quinolylphosphine ligands.
Scheme 23: Synthesis of N-(triazolylmethyl)phosphanamine ligands.
Figure 2: Triazolylphosphanamine ligands synthesized by Wassenaar’s method [22].
Scheme 24: Synthesis of oxazaphosphorines.
Scheme 25: Synthesis of paracyclophane pyridylphosphine ligands.
Scheme 26: Synthesis of triazolylphosphine ligands.
Figure 3: Click-phosphine ligands.
Scheme 27: Ferrocenyl pyridylphosphine imine ligands.
Scheme 28: Synthesis of phosphinooxazolines (PHOX).
Scheme 29: Synthesis of ferrocenylphosphine oxazoles.
Beilstein J. Org. Chem. 2019, 15, 1722–1757, doi:10.3762/bjoc.15.168
Graphical Abstract
Figure 1: Examples of three-carbon chirons.
Figure 2: Structures of derivatives of N-(1-phenylethyl)aziridine-2-carboxylic acid 5–8.
Figure 3: Synthetic equivalency of aziridine aldehydes 6.
Scheme 1: Synthesis of N-(1-phenylethyl)aziridine-2-carboxylates 5. Reagents and conditions: a) TEA, toluene,...
Scheme 2: Absolute configuration at C2 in (2S,1'S)-5a. Reagents and conditions: a) 20% HClO4, 80 °C, 30 h the...
Scheme 3: Major synthetic strategies for a 2-ketoaziridine scaffold [R* = (R)- or (S)-1-phenylethyl; R′ = Alk...
Scheme 4: Synthesis of cyanide (2S,1'S)-13. Reagents and conditions: a) NH3, EtOH/H2O, rt, 72 h; b) Ph3P, CCl4...
Scheme 5: Synthesis of key intermediates (R)-16 and (R)-17 for (R,R)-formoterol (14) and (R)-tamsulosin (15)....
Scheme 6: Synthesis of mitotic kinesin inhibitors (2R/S,1'R)-23. Reagents and conditions: a) H2, Pd(OH)2, EtO...
Scheme 7: Synthesis of (R)-mexiletine ((R)-24). Reagents and conditions: a) TsCl, TEA, DMAP, CH2Cl2, rt, 1 h;...
Scheme 8: Synthesis of (−)-cathinone ((S)-27). Reagents and conditions: a) PhMgBr, ether, 0 °C; b) H2, 10% Pd...
Scheme 9: Synthesis of N-Boc-norpseudoephedrine ((1S,2S)-(+)-29) and N-Boc-norephedrine ((1R,2S)-29). Reagent...
Scheme 10: Synthesis of (−)-ephedrine ((1R,2S)-31). Reagents and conditions: a) TfOMe, MeCN then NaBH3CN, rt; ...
Scheme 11: Synthesis of xestoaminol C ((2S,3R)-35), 3-epi-xestoaminol C ((2S,3S)-35) and N-Boc-spisulosine ((2S...
Scheme 12: Synthesis of ʟ-tryptophanol ((S)-41). Reagents and conditions: a) CDI, MeCN, rt, 1 h then TMSI, MeC...
Scheme 13: Synthesis of ʟ-homophenylalaninol ((S)-42). Reagents and conditions: a) NaH, THF, 0 °C to −78 °C, 1...
Scheme 14: Synthesis of ᴅ-homo(4-octylphenyl)alaninol ((R)-47) and a sphingolipid analogue (R)-48. Reagents an...
Scheme 15: Synthesis of florfenicol ((1R,2S)-49). Reagents and conditions: a) (S)-1-phenylethylamine, TEA, MeO...
Scheme 16: Synthesis of natural tyroscherin ((2S,3R,6E,8R,10R)-55). Reagents and conditions: a) I(CH2)3OTIPS, t...
Scheme 17: Syntheses of (−)-hygrine (S)-61, (−)-hygroline (2S,2'S)-62 and (−)-pseudohygroline (2S,2'R)-62. Rea...
Scheme 18: Synthesis of pyrrolidine (3S,3'R)-68, a fragment of the fluoroquinolone antibiotic PF-00951966. Rea...
Scheme 19: Synthesis of sphingolipid analogues (R)-76. Reagents and conditions: a) BnBr, Mg, THF, reflux, 6 h;...
Scheme 20: Synthesis of ᴅ-threo-PDMP (1R,2R)-81. Reagents and conditions: a) TMSCl, NaI, MeCN, rt, 1 h 50 min,...
Scheme 21: Synthesis of the sphingolipid analogue SG-14 (2S,3S)-84. Reagents and conditions: a) LiAlH4, THF, 0...
Scheme 22: Synthesis of the sphingolipid analogue SG-12 (2S,3R)-88. Reagents and conditions: a) 1-(bromomethyl...
Scheme 23: Synthesis of sphingosine-1-phosphate analogues DS-SG-44 and DS-SG-45 (2S,3R)-89a and (2S,3R)-89a. R...
Scheme 24: Synthesis of N-Boc-safingol ((2S,3S)-95) and N-Boc-ᴅ-erythro-sphinganine ((2S,3R)-95). Reagents and...
Scheme 25: Synthesis of ceramide analogues (2S,3R)-96. Reagents and conditions: a) NaBH4, ZnCl2, MeOH, −78 °C,...
Scheme 26: Synthesis of orthogonally protected serinols, (S)-101 and (R)-102. Reagents and conditions: a) BnBr...
Scheme 27: Synthesis of N-acetyl-3-phenylserinol ((1R,2R)-105). Reagents and conditions: a) AcOH, CH2Cl2, refl...
Scheme 28: Synthesis of (S)-linezolid (S)-107. Reagents and conditions: a) LiAlH4, THF, 0 °C to reflux; b) Boc2...
Scheme 29: Synthesis of (2S,3S,4R)-2-aminooctadecane-1,3,4-triol (ᴅ-ribo-phytosphingosine) (2S,3S,4R)-110. Rea...
Scheme 30: Syntheses of ᴅ-phenylalanine (R)-116. Reagents and conditions: a) AcOH, CH2Cl2, reflux, 4 h; b) MsC...
Scheme 31: Synthesis of N-Boc-ᴅ-3,3-diphenylalanine ((R)-122). Reagents and conditions: a) PhMgBr, THF, −78 °C...
Scheme 32: Synthesis of ethyl N,N’-di-Boc-ʟ-2,3-diaminopropanoate ((S)-125). Reagents and conditions: a) NaN3,...
Scheme 33: Synthesis of the bicyclic amino acid (S)-(+)-127. Reagents and conditions: a) BF3·OEt2, THF, 60 °C,...
Scheme 34: Synthesis of lacosamide, (R)-2-acetamido-N-benzyl-3-methoxypropanamide (R)-130. Reagents and condit...
Scheme 35: Synthesis of N-Boc-norfuranomycin ((2S,2'R)-133). Reagents and conditions: a) H2C=CHCH2I, NaH, THF,...
Scheme 36: Synthesis of MeBmt (2S,3R,4R,6E)-139. Reagents and conditions: a) diisopropyl (S,S)-tartrate (E)-cr...
Scheme 37: Synthesis of (+)-polyoxamic acid (2S,3S,4S)-144. Reagents and conditions: a) AD-mix-α, MeSO2NH2, t-...
Scheme 38: Synthesis of the protected 3-hydroxy-ʟ-glutamic acid (2S,3R)-148. Reagents and conditions: a) LiHMD...
Scheme 39: Synthesis of (+)-isoserine (R)-152. Reagents and conditions: a) AcCl, MeCN, rt, 0.5 h then Na2CO3, ...
Scheme 40: Synthesis of (3R,4S)-N3-Boc-3,4-diaminopentanoic acid (3R,4S)-155. Reagents and conditions: a) Ph3P...
Scheme 41: Synthesis of methyl (2S,3S,4S)-4-(dimethylamino)-2,3-dihydroxy-5-methoxypentanoate (2S,3S,4S)-159. ...
Scheme 42: Syntheses of methyl (3S,4S) 4,5-di-N-Boc-amino-3-hydroxypentanoate ((3S,4S)-164), methyl (3S,4S)-4-N...
Scheme 43: Syntheses of (3R,5S)-5-(aminomethyl)-3-(4-methoxyphenyl)dihydrofuran-2(3H)-one ((3R,5S)-168). Reage...
Scheme 44: Syntheses of a series of imidazolin-2-one dipeptides 175–177 (for R' and R'' see text). Reagents an...
Scheme 45: Syntheses of (2S,3S)-N-Boc-3-hydroxy-2-hydroxymethylpyrrolidine ((2S,3S)-179). Reagents and conditi...
Scheme 46: Syntheses of enantiomers of 1,4-dideoxy-1,4-imino-ʟ- and -ᴅ-lyxitols (2S,3R,4S)-182 and (2R,3S,4R)-...
Scheme 47: Synthesis of 1,4-dideoxy-1,4-imino-ʟ-ribitol (2S,3S,4R)-182. Reagents and conditions: a) AcOH, CH2Cl...
Scheme 48: Syntheses of 1,4-dideoxy-1,4-imino-ᴅ-arabinitol (2R,3R,4R)-182 and 1,4-dideoxy-1,4-imino-ᴅ-xylitol ...
Scheme 49: Syntheses of natural 2,5-imino-2,5,6-trideoxy-ʟ-gulo-heptitol ((2S,3R,4R,5R)-184) and its C4 epimer...
Scheme 50: Syntheses of (−)-dihydropinidine ((2S,6R)-187a) (R = C3H7) and (2S,6R)-isosolenopsins (2S,6R)-187b ...
Scheme 51: Syntheses of (+)-deoxocassine ((2S,3S,6R)-190a, R = C12H25) and (+)-spectaline ((2S,3S,6R)-190b, R ...
Scheme 52: Synthesis of (−)-microgrewiapine A ((2S,3R,6S)-194a) and (+)-microcosamine A ((2S,3R,6S)-194b). Rea...
Scheme 53: Syntheses of ʟ-1-deoxynojirimycin ((2S,3S,4S,5R)-200), ʟ-1-deoxymannojirimycin ((2S,3S,4S,5S)-200) ...
Scheme 54: Syntheses of 1-deoxy-ᴅ-galacto-homonojirimycin (2R,3S,4R,5S)-211. Reagents and conditions: a) MeONH...
Scheme 55: Syntheses of 7a-epi-hyacinthacine A1 (1S,2R,3R,7aS)-220. Reagents and conditions: a) TfOTBDMS, 2,6-...
Scheme 56: Syntheses of 8-deoxyhyacinthacine A1 ((1S,2R,3R,7aR)-221). Reagents and conditions: a) H2, Pd/C, PT...
Scheme 57: Syntheses of (+)-lentiginosine ((1S,2S,8aS)-227). Reagents and conditions: a) (EtO)2P(O)CH2COOEt, L...
Scheme 58: Syntheses of 8-epi-swainsonine (1S,2R,8S,8aR)-231. Reagents and conditions: a) Ph3P=CHCOOMe, MeOH, ...
Scheme 59: Synthesis of a protected vinylpiperidine (2S,3R)-237, a key intermediate in the synthesis of (−)-sw...
Scheme 60: Synthesis of a modified carbapenem 245. Reagents and conditions: a) AcOEt, LiHMDS, THF, −78 °C, 1.5...
Beilstein J. Org. Chem. 2017, 13, 348–371, doi:10.3762/bjoc.13.39
Graphical Abstract
Figure 1: Structures of clinically-relevant polyketides: erythromycin A (1), azithromycin (2), clarithromycin...
Figure 2: Schematic of erythromycin A (1) bound to 23S ribosomal RNA of the 50S subunit of the Deinococcus ra...
Figure 3: Schematic of the biosynthetic pathway leading to erythromycin A (1) in the bacterium Saccharopolysp...
Figure 4: Schematic of the virginiamycin PKS from Streptomyces virginiae, a member of the trans-AT PKS family ...
Figure 5: Determination of the stereochemistry of extender unit selection by the AT domains of modular PKS. a...
Figure 6: Creation by genetic engineering of the DEBS 1-TE model system. The region of the eryAIII gene encod...
Figure 7: Model for substrate selection by AT domains. a) Sequence motifs in malonyl- and methylmalonyl-CoA-s...
Figure 8: Proposed mechanism for KS-catalyzed chain extension, based on extrapolation from studies on homolog...
Figure 9: Experiment in vitro to determine the stereochemistry of condensation in modular PKS [46]. Use of specif...
Figure 10: Genetic engineering experiments which suggested a role for the KS domain in epimerization. a) A dik...
Figure 11: Models for control of the stereochemistry of reduction by KR domains. The two directions of ketored...
Figure 12: Assays in vitro to evaluate the stereospecificity of recombinant KR domains. A series of KR domains...
Figure 13: Assays in vitro which provided the first direct evidence that KR domains act as epimerases [77]. Biosyn...
Figure 14: Assays in vitro to demonstrate directly the epimerase activity of PKS KR domains. a) Equilibrium ex...
Figure 15: Model for DH-catalyzed generation of trans and cis double bonds by syn elimination from substrates ...
Figure 16: Stereospecificity of dehydration by Rif DH10 [94]. a) The four possible diastereomeric diketide-ACP sub...
Figure 17: Stereocontrol by PKS ER domains. Sequence motifs correlated with the final stereochemistry of the C...
Figure 18: a) PKS engineered to test the role of the ER stereospecificity residues [115]. TKS-ERY4 was created by r...
Beilstein J. Org. Chem. 2014, 10, 2367–2376, doi:10.3762/bjoc.10.247
Graphical Abstract
Figure 1: Structures of the repeating unit of MenX CPS and synthetic oligomers 1–3.
Scheme 1: Reagents and conditions: a) NiCl2/NaBH4, MeOH; b) Ac2O, 86% over 2 steps; c) TBAF, THF, −40 °C to r...
Scheme 2: Reagents and conditions: a) PivCl in pyridine, then I2 in 19:1 pyridine/H2O, then 1 M TEAB (45%); b...
Scheme 3: Reagents and conditions: a) SIDEA, Et3N, DMSO: 11 (64%), 12 (49%), 13 (51%); b) CRM197, 100 mM NaPi...
Figure 2: IgG levels detected at OD = 1 in individual post 3 sera (sera collected two weeks after the third i...
Figure 3: A) IgG levels detected at OD = 1 in individual post 3 sera of BALB/c mice immunization at 0.3 μg sa...
Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106
Graphical Abstract
Scheme 1: Synthesis of P-stereogenic phosphines 5 using menthylphosphinite borane diastereomers 2.
Scheme 2: Enantioselective synthesis of chiral phosphines 10 with ephedrine as a chiral auxiliary.
Scheme 3: Chlorophosphine boranes 11a as P-chirogenic electrophilic building blocks.
Scheme 4: Monoalkylation of phenylphosphine borane 15 with methyl iodide in the presence of Cinchona alkaloid...
Scheme 5: Preparation of tetraphosphine borane 19.
Scheme 6: Using chiral chlorophosphine-boranes 11b as phosphide borane 20 precursors.
Scheme 7: Nickel-catalyzed cross-coupling (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 8: Pd-catalyzed cross-coupling reaction with organophosphorus stannanes 30.
Scheme 9: Copper iodide catalyzed carbon–phosphorus bond formation.
Scheme 10: Thermodynamic kinetic resolution as the origin of enantioselectivity in metal-catalyzed asymmetric ...
Scheme 11: Ru-catalyzed asymmetric phosphination of benzyl and alkyl chlorides 35 with HPPhMe (36a, PHOX = pho...
Scheme 12: Pt-catalyzed asymmetric alkylation of secondary phosphines 36b.
Scheme 13: Different adducts 43 can result from hydrophosphination.
Scheme 14: Pt-catalyzed asymmetric hydrophosphination.
Scheme 15: Intramolecular hydrophosphination of phosphinoalkene 47.
Scheme 16: Organocatalytic asymmetric hydrophosphination of α,β-unsaturated aldehydes 59.
Scheme 17: Preparation of phosphines using zinc organometallics.
Scheme 18: Preparation of alkenylphosphines 71a from alkenylzirconocenes 69 (dtc = N,N-diethyldithiocarbamate,...
Scheme 19: SNAr with P-chiral alkylmethylphosphine boranes 13c.
Scheme 20: Synthesis of QuinoxP 74 (TMEDA = tetramethylethylenediamine).
Scheme 21: Pd-Mediated couplings of a vinyl triflate 76 with diphenylphosphine borane 13e.
Figure 1: Menthone (83) and camphor (84) derived chiral phosphines.
Scheme 22: Palladium-catalyzed cross-coupling reaction of vinyl tosylates 85 and 87 with diphenylphosphine bor...
Scheme 23: Attempt for the enantioselective palladium-catalyzed C–P cross-coupling reaction between an alkenyl...
Scheme 24: Enol phosphates 88 as vinylic coupling partners in the palladium-catalyzed C–P cross-coupling react...
Scheme 25: Nickel-catalyzed cross-coupling in the presence of zinc (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 26: Copper-catalyzed coupling of secondary phosphines with vinyl halide 94.
Scheme 27: Palladium-catalyzed cross-coupling of aryl iodides 97 with organoheteroatom stannanes 30.
Scheme 28: Synthesis of optically active phosphine boranes 100 by cross-coupling with a chiral phosphine boran...
Scheme 29: Palladium-catalyzed P–C cross-coupling reactions between primary or secondary phosphines and functi...
Scheme 30: Enantioselective synthesis of a P-chirogenic phosphine 108.
Scheme 31: Enantioselective arylation of silylphosphine 110 ((R,R)-Et-FerroTANE = 1,1'-bis((2R,4R)-2,4-diethyl...
Scheme 32: Nickel-catalyzed arylation of diphenylphosphine 25d.
Scheme 33: Nickel-catalyzed synthesis of (R)-BINAP 116 (dppe = 1,2-bis(diphenylphosphino)ethane, DABCO = 1,4-d...
Scheme 34: Nickel-catalyzed cross-coupling between aryl bromides 119 and diphenylphosphine (25d) (dppp = 1,3-b...
Scheme 35: Stereocontrolled Pd(0)−Cu(I) cocatalyzed aromatic phosphorylation.
Scheme 36: Preparation of alkenylphosphines by hydrophosphination of alkynes.
Scheme 37: Palladium and nickel-catalyzed addition of P–H to alkynes 125a.
Scheme 38: Palladium-catalyzed asymmetric hydrophosphination of an alkyne 128.
Scheme 39: Ruthenium catalyzed hydrophosphination of propargyl alcohols 132 (cod = 1,5-cyclooctadiene).
Scheme 40: Cobalt-catalyzed hydrophosphination of alkynes 134a (acac = acetylacetone).
Scheme 41: Tandem phosphorus–carbon bond formation–oxyfunctionalization of substituted phenylacetylenes 125c (...
Scheme 42: Organolanthanide-catalyzed intramolecular hydrophosphination/cyclization of phosphinoalkynes 143.
Scheme 43: Hydrophosphination of alkynes 134c catalyzed by ytterbium-imine complexes 145 (hmpa = hexamethylpho...
Scheme 44: Calcium-mediated hydrophosphanylation of alkyne 134d.
Scheme 45: Formation and substitution of bromophosphine borane 151.
Scheme 46: General scheme for a nickel or copper catalyzed cross-coupling reaction.
Scheme 47: Copper-catalyzed synthesis of alkynylphosphines 156.
Beilstein J. Org. Chem. 2014, 10, 442–448, doi:10.3762/bjoc.10.41
Graphical Abstract
Figure 1: A family of chiral and achiral equivalents of nucleophilic glycine.
Scheme 1: Synthesis of chiral ligands 4a–f.
Scheme 2: Preparation of diastereomeric Ni(II) complexes 5a–f and 6a–f.
Figure 2: Crystallographic structure of (SCRN)-5b.
Figure 3: Crystallographic structure of (SCRN)-5b showing an exposure of the methyl moiety of α-phenylethylam...
Beilstein J. Org. Chem. 2013, 9, 2120–2128, doi:10.3762/bjoc.9.249
Graphical Abstract
Scheme 1: Synthesis of 3-halo-2H-chromenes.
Figure 1: X-ray molecular structure of 2f.
Scheme 2: Gram-scale synthesis of 2f.
Scheme 3: Retaining propargylic chirality.
Scheme 4: Mechanistic basis postulated for the synthesis of 2.
Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119
Graphical Abstract
Figure 1: Photoisomerization process of azobenzene.
Figure 2: Representative example of an UV spectrum of an azocompound of the azobenzene type (blue line: trans...
Figure 3: Mechanistic proposals for the isomerization of azobenzenes.
Figure 4: Representation of the photocontrol of a K+ channel in the cellular membrane based on the isomerizat...
Figure 5: (a) MAG interaction with iGluR; (b) photocontrol of the opening of the ion channel by trans–cis iso...
Figure 6: Photocontrol of the structure of the α-helix in the polypeptide azoderivative 2. Reprinted (adapted...
Figure 7: Recognition of a guanidinium ion by a cis,cis-bis-azo derivative 3.
Figure 8: Recognition of cesium ions by cis-azo derivative 4.
Figure 9: Photocontrolled formation of an inclusion complex of cyclodextrin trans-azo 5+6.
Figure 10: Pseudorotaxane-based molecular machine.
Figure 11: Molecular hinge. Reprinted (adapted) with permission from Org. Lett. 2004, 6, 2595–2598. Copyright ...
Figure 12: Molecular threader. Reprinted (adapted) with permission from Acc. Chem. Res. 2001, 34, 445–455. Cop...
Figure 13: Molecular scissors based on azobenzene 12. Reprinted (adapted) with permission from J. Am. Chem. So...
Figure 14: Molecular pedals. Reprinted by permission from Macmillan Publishers Ltd: Nature, 2006, 440, 512–515...
Figure 15: Design of nanovehicles based on azo structures. Reprinted (adapted) with permission from Org. Lett. ...
Figure 16: Light-activated mesostructured silica nanoparticles (LAMs).
Figure 17: Molecular lift.
Figure 18: Conformational considerations in mono-ortho-substituted azobenzenes.
Scheme 1: Synthesis and photoisomerization of sulfinyl azobenzenes. Reprinted (adapted) with permission from ...
Figure 19: Photoisomerization of azocompound 22 and its application as a photobase catalyst.
Figure 20: Effect of irradiation with linearly polarized light on azo-LCEs. Reprinted by permission from Macmi...
Figure 21: Chemically and photochemically triggered memory switching cycle of the [2]rotaxane 25.
Figure 22: Unidirectional photoisomerization process of the azobenzene 26.
Beilstein J. Org. Chem. 2011, 7, 1327–1333, doi:10.3762/bjoc.7.156
Graphical Abstract
Scheme 1: Desymmetrising metallation for the enantioselective synthesis of atropisomers.
Scheme 2: Benzylic lithiation of a diaryl ether.
Scheme 3: Benzylic metallation of a diaryl ether α to a carbamate.
Scheme 4: Diastereo- and enantioselective synthesis of atropisomeric ethers by benzylic lithiation.
Scheme 5: Atroposelective stannylation.
Scheme 6: Stereospecific tin–lithium exchange/quench reactions.
Scheme 7: Proposed stereochemical pathway.
Beilstein J. Org. Chem. 2011, 7, 615–621, doi:10.3762/bjoc.7.72
Graphical Abstract
Scheme 1: Stereogenic boron in resolved acyclic and cyclic complexes 1–4.
Scheme 2: Synthesis of the racemic boronate–imine complex 8 and boronate–amine complex 10. Reagents and condi...
Figure 1: Solid-state structure of boronate–imine complex 8 (a) and the chosen asymmetric unit of the crystal...
Figure 2: Superposition of the skeletons of boronate complexes 8 (red) and 10 (green).
Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68
Graphical Abstract
Figure 1: Seven out of the ten top selling drugs in the USA in 2009 contain sulfur. Figures in italics are to...
Figure 2: Naturally occurring organosulfur compounds glutathione and (R)-thioterpineol.
Figure 3: Methods for the synthesis of chiral tertiary thiol 1.
Scheme 1: Preparation of thioethers 4 from α-hydroxy esters.
Scheme 2: Nucleophilic substitution in α-aryl-α-hydroxy esters.
Scheme 3: Preparation of α,α-dialkylthioethers.
Scheme 4: Preparation of α-cyanothioacetate 12.
Scheme 5: Synthesis of (R)-(+)-spirobrassinin.
Scheme 6: Opening of cyclic sulfamidates with thiol nucleophiles.
Scheme 7: Synthesis of androgen 20.
Scheme 8: Synthesis of (+)-BE-52440A.
Scheme 9: The Mitsunobu reaction.
Scheme 10: Mitsunobu substitution at a quaternary centre.
Figure 4: Initially assigned structure of hexacyclinol.
Scheme 11: Preparation of thioether 29.
Scheme 12: Thioethers 33 prepared from phosphinites 31.
Scheme 13: Preparation of enantiomerically pure thiol 39.
Scheme 14: Thioethers prepared by a modified Mitsunobu reaction.
Scheme 15: Nucleophilic conjugate addition.
Scheme 16: Asymmetric addition to cyclic enones.
Scheme 17: Preparation of thioether 45.
Scheme 18: Catalytic kinetic resolution of the enantiomers of enone 46.
Scheme 19: Organocatalytic conjugate addition to nitroalkenes 49.
Scheme 20: Preparation of β-amino acid 54.
Scheme 21: Sulfur migration within oxazolidine-2-thiones 56.
Scheme 22: Preparation of thiols 62 by self-regeneration of stereocentres.
Scheme 23: Synthesis of (5R)-thiolactomycin.
Scheme 24: Preparation of tertiary thiols and thioethers via α-thioorganolithiums.
Scheme 25: Diastereoselective methylation of organolithium 71.
Scheme 26: Addition to lithiated thiocarbamate 75.
Scheme 27: Configurational lability in unhindered α-lithiothiocarbamates.
Scheme 28: Configurational stability in bulky α-lithiothiocarbamates.
Scheme 29: Asymmetric functionalisation of secondary benzylic thiocarbamates.
Scheme 30: Methylation of lithioallyl thiocarbamates.
Scheme 31: Asymmetric preparation of tertiary allylic thiols.
Scheme 32: Asymmetric preparation of thiols 96 by aryl migration in lithiated thiocarbamates.
Beilstein J. Org. Chem. 2011, 7, 496–502, doi:10.3762/bjoc.7.58
Graphical Abstract
Scheme 1: Synthesis of 5-aryl-11H-benzo[b]fluorenes via benzannulated enyne–allenes.
Scheme 2: Synthesis of 1,1'-binaphthyl-substituted 11H-benzo[b]fluorene 3c.
Scheme 3: Synthesis of 5-(2-methoxyphenyl)- and 5-[2-(methoxymethyl)phenyl]-11H-benzo[b]fluorene 13a and 13b.
Scheme 4: Synthesis of 5-(1-naphthyl)- and 5-(2-methoxy-1-naphthyl)-11H-benzo[b]fluorene 20a and 20b.
Scheme 5: Synthesis of 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene 20c.
Scheme 6: Demethylation of 22b to form 5-(2-hydroxy-1-naphthyl)-11H-benzo[b]fluorene 24.
Beilstein J. Org. Chem. 2009, 5, No. 33, doi:10.3762/bjoc.5.33
Graphical Abstract
Scheme 1: Aziridine containing natural products.
Scheme 2: Mitomycin structures and nomenclature.
Scheme 3: Base catalysed epimerization of mitomycin B.
Scheme 4: Biosynthesis of mitomycin C (MMC) 7.
Scheme 5: Mode of action of mitomycin C.
Scheme 6: The N–C3–C9a disconnection.
Scheme 7: Danishefsky’s Retrosynthesis of mitomycin K.
Scheme 8: Hetero Diels–Alder reaction en route to mitomycins.
Scheme 9: Nitroso Diels–Alder cycloaddition.
Scheme 10: Frank azide cycloadddition.
Scheme 11: Final steps of mitomycin K synthesis. aPDC, DCM; bPhSCH2N3, PhH, 80 °C; cL-selectride, THF, −78 °C; ...
Scheme 12: Naruta–Maruyama retrosynthesis.
Scheme 13: Synthesis of a leucoaziridinomitosane by nitrene cycloaddition. aAlCl3-Et2O; bNaH, ClCH2OMe; cn-BuL...
Scheme 14: Thermal decomposition of azidoquinone 51.
Scheme 15: Diastereoselectivity during the cycloaddition.
Scheme 16: Oxidation with iodo-azide.
Scheme 17: Williams’ approach towards mitomycins.aDEIPSCl, Imidazole, DCM; bPd/C, HCO2NH4, MeOH; cAllocCl, NaH...
Scheme 18: Synthesis of pyrrolidones by homoconjugate addition.
Scheme 19: Homoconjugate addition on the fully functionalized substrate.
Scheme 20: Introduction of the olefin.
Scheme 21: Retrosynthesis of N–C9a, N–C3 bond formation.
Scheme 22: Synthesis of the pyrrolo[1,2]indole 82 using N-PSP activation.aAc2O, Py; bAc2O, Hg(OAc)2, AcOH, 90%...
Scheme 23: Synthesis of an aziridinomitosane. am-CPBA, DCM then iPr2NH, CCl4 reflux; bK2CO3, MeOH; cBnBr, KH; d...
Scheme 24: Oxidation products of a leucoaziridinomitosane obtained from a Polonovski oxidation.
Scheme 25: Polonovski oxidation of an aziridinomitosane. am-CPBA; bPd/C, H2; cDimethoxypropane, PPTS.
Scheme 26: The C1–C9a disconnection.
Scheme 27: Ziegler synthesis of desmethoxymitomycin A.aIm2C=O, THF; bNH3; cTMSOTf, 2,6-di-tert-butylpyridine, ...
Scheme 28: Transformation of sodium erythorbate.aTBDMSCl; bNaN3; cPPh3; d(Boc)2O, DMAP; eTBAF; fTf2O, Pyr.
Scheme 29: Formation of C9,C10-unsaturation in the mitomycins. am-CPBA, DCM; bO3, MeOH; cMe2S; dKHMDS, (EtO)3P...
Scheme 30: Fragmentation mechanism.
Scheme 31: Michael addition-cyclisation.
Scheme 32: SmI2 8-endo-dig cyclisation.
Scheme 33: Synthesis of pyrrolo[1,2-a]indole by 5-exo-dig radical cyclization.
Scheme 34: The C9–C9a disconnection.
Scheme 35: Intramolecular nitrile oxide cycloaddition.
Scheme 36: Regioselectivity of the INOC.
Scheme 37: Fukuyama’s INOC strategy.
Scheme 38: Synthesis of a mitosane core by rearrangement of a 1-(1-pyrrolidinyl)-1,3-butadiene.
Scheme 39: Sulikowski synthesis of an aziridinomitosene. aPd(Tol3P)2Cl2, Bu3SnF, 140; bH2, Pd/C; cTFAA, Et3N; d...
Scheme 40: Enantioselective carbene insertion.
Scheme 41: Parson’s radical cyclization.
Scheme 42: Cha’s mitomycin B core synthesis.
Scheme 43: The N-aromatic disconnection.
Scheme 44: Kishi retrosynthesis.
Scheme 45: Kishi synthesis of a starting material. aallyl bromide, K2CO3, acetone, reflux; bN,N-Dimethylanilin...
Scheme 46: Kishi synthesis of MMC 7. aLDA, THF, −78 °C then PhSeBr, THF, −78 °C; bH2O2, THF-EtOAc; cDIBAL, DCM...
Scheme 47: Acid catalyzed degradation of MMC 7.
Scheme 48: In vivo formation of apomitomycin B.
Scheme 49: Advanced intermediate for apomitomycin B synthesis.
Scheme 50: Remers synthesis of a functionalized mitosene. aTMSCl, Et3N, ZnCl2 then NBS; bAcOK; cNH2OH; dPd/C, H...
Scheme 51: Coleman synthesis of desmethoxymitomycin A. aSnCl2, PhSH, Et3N, CH3CN; bClCO2Bn, Et3N; cPPh3, DIAD,...
Scheme 52: Transition state and pyrrolidine synthesis.
Scheme 53: Air oxidation of mitosanes and aziridinomitosanes.
Scheme 54: The C9-aromatic disconnection.
Scheme 55: Synthesis of the aziridine precursor. aLHMDS, THF; bNaOH; c(s)-α-Me-BnNH2, DCC, HOBT; dDIBAL; eK2CO3...
Scheme 56: Synthesis of 206 via enamine conjugate addition.
Scheme 57: Rapoport synthesis of an aziridinomitosene.
Scheme 58: One pot synthesis of a mitomycin analog.
Scheme 59: Synthesis of compound 218 via intramolecular Heck coupling. aEtMgCl, THF, then 220; bMsCl, Et3N; cN...
Scheme 60: Elaboration of indole 223. aEt3N, Ac2O; bAcOH; cSOCl2, Et3N; dNaN3, DMF; eH2SO4, THF; fK2CO3, MeOH; ...
Scheme 61: C9-C9a functionalization from indole.
Scheme 62: Synthesis of mitomycin K. a2 equiv. MoO5.HMPA, MeOH; bPPh3, Et3N, THF-H2O; cMeOTf, Py, DCM; dMe3SiCH...
Scheme 63: Configurational stability of mitomycin K derivatives.
Scheme 64: Epimerization of carbon C9a in compound 227b.
Scheme 65: Corey–Chaykovsky synthesis of indol 235.
Scheme 66: Cory intramolecular aza-Darzens reaction for the formation of aziridinomitosene 239.
Scheme 67: Jimenez synthesis of aziridinomitosene 242.
Scheme 68: Von Braun opening of indoline 244.
Scheme 69: C9a oxidation of an aziridinomitosane with DDQ/OsO4.
Scheme 70: Synthesis of epi-mitomycin K. aNaH, Me2SO4; bH2, Pd/C; cMitscher reagent [165]; d[(trimethylsilyl)methyl...
Scheme 71: Mitomycins rearrangement.
Scheme 72: Fukuyama’s retrosynthesis.
Scheme 73: [2+3] Cycloaddition en route to isomitomycin A. aToluene, 110 °C; bDIBAL, THF, −78 °C; cAc2O, Py.; d...
Scheme 74: Final steps of Fukuyama’s synthesis.
Scheme 75: “Crisscross annulation”.
Scheme 76: Synthesis of 274; the 8-membered ring 274 was made using a crisscross annulation. a20% Pd(OH)2/C, H2...
Scheme 77: Conformational analysis of compound 273 and 275.
Scheme 78: Synthesis of a mitomycin analog. aNa2S2O4, H2O, DCM; bBnBr (10 equiv), K2CO3, 18-crown-6 (cat.), TH...
Scheme 79: Vedejs retrosynthesis.
Scheme 80: Formation of the azomethine ylide.
Scheme 81: Vedejs second synthesis of an aziridinomitosene. aDIBAL; bTPAP, NMO; c287; dTBSCl, imidazole.
Scheme 82: Trityl deprotection and new aziridine protecting group 300.
Scheme 83: Ene reaction towards benzazocinones.
Scheme 84: Benzazocenols via homo-Brook rearrangement.
Scheme 85: Pt-catalyzed [3+2] cycloaddition.
Scheme 86: Carbonylative lactamization entry to benzazocenols. aZn(OTf)2, (+)-N-methylephedrine, Et3N, TMS-ace...
Scheme 87: 8 membered ring formation by RCM. aBOC2O, NaHCO3; bTBSCl, Imidazole, DMF; callyl bromide, NaH, DMF; ...
Scheme 88: Aziridinomitosene synthesis. aTMSN3; bTFA; cPOCl3, DMF; dNaClO2, NaH2PO4, 2-methyl-2-butene; eMeI, ...
Scheme 89: Metathesis from an indole.
Scheme 90: Synthesis of early biosynthetic intermediates of mitomycins.
Beilstein J. Org. Chem. 2008, 4, No. 2, doi:10.1186/1860-5397-4-2
Graphical Abstract
Figure 1: (–)-Indolizidine 167B.
Scheme 1: Reagents: i Rh4(CO)12, 30 atm CO:H2 = 1:1, 125 °C, toluene, 24 min, 76% yield; ii the same conditio...
Scheme 2: Stereospecific interconversion of the rhodium-alkyl intermediates as the key for regioselective for...