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Search for "MacMillan catalyst" in Full Text gives 4 result(s) in Beilstein Journal of Organic Chemistry.
Modern synthetic pathways towards eribulin and its subunits
- Sebastian Dominik Graf
Beilstein J. Org. Chem. 2026, 22, 495–526, doi:10.3762/bjoc.22.37
- -Tol2IOTf led to the formation of salt 239. Additionally, building block 247 was synthesized from commercial 240 (Scheme 27). Again, stereoselective chlorination using NCS and MacMillan catalyst 248 was perfomed to yield 241 [101]. Subsequently, ketone 249 was added to aldehyde 241 within a stereoselective
Graphical Abstract
Figure 1: Eribulin with common synthetic precursor fragments and halichondrin B.
Scheme 1: Overview of the industrial process pathway for the large-scale production of the mesylate salt of 1...
Scheme 2: Synthesis of 22. (a) i. 2,2-dimethoxypropane, p-TsOH, MeOH, 65 °C; ii. NaBH4, MeOH, rt; (b) i. NaH,...
Scheme 3: Synthesis of 27. (a) i. NaH, BnBr, THF, rt; ii. iodobenzoic acid, MeCN, 80 °C; iii. (EtO)2POCH2COOE...
Scheme 4: Synthesis of 31 and 33. (a) i. MMTrCl, iPr2NEt, DCM, rt; ii. K2CO3, MeOH, DCM, rt; iii. TBDMSCl, im...
Scheme 5: Synthesis of 1. (a) CrCl2, 37, 38, 39 (proton sponge), LiCl, Mn, ZrCp2Cl2, MeCN, EtOAc; (b) SrCO3, t...
Scheme 6: Synthesis of 45. Above: Reaction conditions: (a) methoxyacetic acid, BF3·OEt2, DCM, −30 °C; (b) Pd(...
Scheme 7: Synthesis of 64. Reaction conditions: (a) i. acetone, I2, rt; ii. vinylmagnesium bromide, THF, −20 ...
Scheme 8: Synthesis of 79. Above: Reaction conditions: (a) i. K2CO3, MeOH, 60 °C; ii. 2,2-dimethoxypropane, H2...
Scheme 9: Synthesis of 92. Reaction conditions: (a) TESCl, imidazole, DCM, 0 °C to rt; (b) i. oxalyl chloride...
Scheme 10: Synthesis of 104. Above: Reaction conditions: (a) cyclohexanone, p-TsOH, toluene, 110 °C, crystalli...
Scheme 11: Synthesis of 117. (a) i. acetone, CuSO4, rt; ii. H2O2, K2CO3, H2O, rt; iii. EtI, MeCN, 70 °C; (b) i...
Scheme 12: Synthesis of 121. Reaction conditions: (a) i. TBDPSCl, imidazole, DMF, rt; ii. O3, DCM, −78 °C; iii...
Scheme 13: Synthesis of 131. (a) i. 2,2-dimethoxypropane, p-TsOH, MeOH, 60 °C; ii. LiAlH4, THF, 0 °C to rt; (b...
Scheme 14: Synthesis of 143. (a) i. I2, PPh3, imidazole, DCM; ii. HMPA, CuI, vinylmagnesium bromide, THF, −20 ...
Scheme 15: Modified synthesis of 104. Reaction conditions: (a) (EtO)2POCH2COOEt, KOt-Bu, THF, 15 °C; (b) TBAF,...
Scheme 16: Synthesis of 161. Reaction conditions: (a) crotyl bromide, Sn, TBAI, NaI, DMF/H2O, rt; (b) NaH, BnB...
Scheme 17: Synthesis of 169. Reaction conditions: (a) i. Co2(CO)8, BF3·Et2O, DCM, 23 °C; ii. CAN, acetone, 0 °...
Scheme 18: Synthesis of 181. Reaction conditions: (a) i. Co2(CO)8, BF3·Et2O, DCM, 23 °C; ii. (NH4)2Ce(NO3)6, a...
Scheme 19: Synthesis of 186. Reaction conditions: (a) NEt3, LiCl, MeCN, 0–23 °C; (b) HF·pyridine, MeCN, 23 °C;...
Scheme 20: Modified synthesis of 181. Reaction conditions: (a) i. Ni(cod)2, P(n-Bu)3, Et3SiH, THF, 23 °C; ii. ...
Scheme 21: Synthesis of 200. Reaction conditions: (a) i. Co2(CO)8, DCM, 23 °C; ii. BF3·Et2O, 0 °C; iii. (NH4)2...
Scheme 22: Modified synthesis of 186. Reaction conditions: (a) DDQ, 2,6-di-t-Bu-4-hydroxytoluene, hv, MeCN, 23...
Scheme 23: Synthesis of 1. Reaction conditions: (a) i. CrCl2, NiCl2, 206, NEt3, THF, 23 °C; ii. DBU, toluene, ...
Scheme 24: Synthesis of 217. Above: Reaction conditions: (a) TBDPSCl, imidazole, DCM, 0–5 °C. (b) m-CPBA, DCM,...
Scheme 25: Synthesis of 231. Reaction conditions: (a) i. AcCl, MeOH, 0 °C to rt; ii. TrCl, pyridine, 50 °C; (b...
Scheme 26: Synthesis of 239. Reaction conditions: (a) i. Boc2O, K2CO3, THF, rt; ii. Ru(acac)3, NaBrO3, EtOAc, H...
Scheme 27: Synthesis of 247. Reaction conditions: (a) NCS, 248, MeCN, 0 °C to rt; (b) LDA, 249, THF, −78 °C; (...
Scheme 28: Synthesis of 255. Reaction conditions: (a) i. LiHMDS, THF, −78 °C to rt; ii. m-CPBA, DCM, −78 °C to...
Scheme 29: Synthesis of 261. Reaction conditions: (a) allyltrimethylsilane, TiCl4, DCM −78 °C; (b) LiBH4, EtOH...
Scheme 30: Synthesis of 265. Reaction conditions: (a) (R,R)-Ru-cat (0.2 mol %), DCM, NEt3, HCOOH, rt; (b) TBAF...
Scheme 31: Synthesis of 272. Reaction conditions: (a) LDA, THF, −78 °C; (b) DMP, NaHCO3, DCM, 0 °C to rt; (c) (...
Scheme 32: Synthesis of 292. Reaction conditions: (a) TsCl, NEt3, DCM, rt; (b) K2CO3, MeOH, 45 °C; (c) vinylma...
Scheme 33: Synthesis of 296. Reaction conditions: (a) 171 (see Scheme 17), Cr-cat, CoPc (see Scheme 17), Mn, NEt3·HCl, LiCl, TMS...
Scheme 34: Synthesis of 299. Reaction conditions: (a) 172 (see Scheme 17), CrCl2, NEt3, NiCl2, THF, rt; (b) KHMDS, THF,...
Scheme 35: Synthesis of 305. Reaction conditions: (a) i. p-TsOH, MeOH, 40 °C; ii. MeLi, LiBr, THF, −25 °C; (b)...
Scheme 36: Synthesis of 1. Reaction conditions: (a) i. 41 (see Scheme 6), LDA, THF, −78 °C; ii. DMP, NaHCO3, DCM, rt; ...
Scheme 37: Synthesis of 324. Reaction conditions: (a) i. acetone, CuSO4, rt; ii. H2O2 (30%), K2CO3, rt; iii. E...
Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts
- Jan Wallbaum and
- Daniel B. Werz
Beilstein J. Org. Chem. 2017, 13, 2577–2583, doi:10.3762/bjoc.13.254
- ; MacMillan catalyst; organocatalysis; Introduction Organocatalytic iminium and enamine activation has attracted organic chemists for more than one century [1]. Until today a wide and constantly increasing number of different organocatalytic transformations with various substrates have been accomplished [2
Graphical Abstract
Scheme 1: a) MacMillan’s enantioselective α-alkylation of aldehydes. b) Our enantioselective 1,3-chlorosulfen...
Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update
- Bin Yu,
- Hui Xing,
- De-Quan Yu and
- Hong-Min Liu
Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98
- -workers described the asymmetric α-alkylation of aldehydes with 3-indolyl-3-hydroxyoxindoles in aqueous medium in the presence of catalytic MacMillan catalyst (10 mol %, cat. 41), affording the desired products in good to excellent yields (62–98%) and with moderate diastereoselectivities (up to 70:30 dr
Graphical Abstract
Figure 1: 3-Hydroxyoxindole-containing natural products and biologically active molecules.
Scheme 1: Chiral CNN pincer Pd(II) complex 1 catalyzed asymmetric allylation of isatins.
Scheme 2: Asymmetric allylation of ketimine catalyzed by the chiral CNN pincer Pd(II) complex 2.
Scheme 3: Pd/L1 complex-catalyzed asymmetric allylation of 3-O-Boc-oxindoles.
Scheme 4: Cu(OTf)2-catalyzed asymmetric direct addition of acetonitrile to isatins.
Scheme 5: Chiral tridentate Schiff base/Cu complex catalyzed asymmetric Friedel–Crafts alkylation of isatins ...
Scheme 6: Guanidine/CuI-catalyzed asymmetric alkynylation of isatins with terminal alkynes.
Scheme 7: Asymmetric intramolecular direct hydroarylation of α-ketoamides.
Scheme 8: Plausible catalytic cycle for the direct hydroarylation of α-ketoamides.
Scheme 9: Ir-catalyzed asymmetric arylation of isatins with arylboronic acids.
Scheme 10: Enantioselective decarboxylative addition of β-ketoacids to isatins.
Scheme 11: Ruthenium-catalyzed hydrohydroxyalkylation of olefins and 3-hydroxy-2-oxindoles.
Scheme 12: Proposed catalytic mechanism and stereochemical model.
Scheme 13: In-catalyzed allylation of isatins with stannylated reagents.
Scheme 14: Modified protocol for the synthesis of allylated 3-hydroxyoxindoles.
Scheme 15: Hg-catalyzed asymmetric allylation of isatins with allyltrimethylsilanes.
Scheme 16: Enantioselective additions of organoborons to isatins.
Scheme 17: Asymmetric aldol reaction of isatins with cyclohexanone.
Scheme 18: Enantioselective aldol reactions of aliphatic aldehydes with isatin derivatives and the plausible t...
Scheme 19: Enantioselective aldol reaction of isatins and 2,2-dimethyl-1,3-dioxan-5-one.
Scheme 20: Asymmetric aldol reactions between ketones and isatins.
Scheme 21: Phenylalanine lithium salt-catalyzed asymmetric synthesis of 3-alkyl-3-hydroxyoxindoles.
Scheme 22: Aldolization between isatins and dihydroxyacetone derivatives.
Scheme 23: One-pot asymmetric synthesis of convolutamydine A.
Scheme 24: Asymmetric aldol reactions of cyclohexanone and acetone with isatins.
Scheme 25: Aldol reactions of acetone with isatins.
Scheme 26: Aldol reactions of ketones with isatins.
Scheme 27: Enantioselective allylation of isatins.
Scheme 28: Asymmetric aldol reaction of trifluoromethyl α-fluorinated β-keto gem-diols with isatins.
Scheme 29: Plausible mechanism proposed for the asymmetric aldol reaction.
Scheme 30: Asymmetric aldol reaction of 1,1-dimethoxyacetone with isatins.
Scheme 31: Enantioselective Friedel-Crafts reaction of phenols with isatins.
Scheme 32: Enantioselective addition of 1-naphthols with isatins.
Scheme 33: Enantioselective aldol reaction between 3-acetyl-2H-chromen-2-ones and isatins.
Scheme 34: Stereoselective Mukaiyama–aldol reaction of fluorinated silyl enol ethers with isatins.
Scheme 35: Asymmetric vinylogous Mukaiyama–aldol reaction between 2-(trimethylsilyloxy)furan and isatins.
Scheme 36: β-ICD-catalyzed MBH reactions of isatins with maleimides.
Scheme 37: β-ICD-catalyzed MBH reactions of 7-azaisatins with maleimides and activated alkenes.
Scheme 38: Enantioselective aldol reaction of isatins with ketones.
Scheme 39: Direct asymmetric vinylogous aldol reactions of allyl ketones with isatins.
Scheme 40: Enantioselective aldol reactions of ketones with isatins.
Scheme 41: The MBH reaction of isatins with α,β-unsaturated γ-butyrolactam.
Scheme 42: Reactions of tert-butyl hydrazones with isatins followed by oxidation.
Scheme 43: Aldol reactions of isatin derivatives with ketones.
Scheme 44: Enantioselective decarboxylative cyanomethylation of isatins.
Scheme 45: Catalytic kinetic resolution of 3-hydroxy-3-substituted oxindoles.
Scheme 46: Lewis acid catalyzed Friedel–Crafts alkylation of 3-hydroxy-2-oxindoles with electron-rich phenols.
Scheme 47: Lewis acid catalyzed arylation of 3-hydroxyoxindoles with aromatics.
Scheme 48: Synthetic application of 3-arylated disubstituted oxindoles in the construction of core structures ...
Scheme 49: CPA-catalyzed dearomatization and arylation of 3-indolyl-3-hydroxyoxindoles with tryptamines and 3-...
Scheme 50: CPA-catalyzed enantioselective decarboxylative alkylation of β-keto acids with 3-hydroxy-3-indolylo...
Scheme 51: BINOL-derived imidodiphosphoric acid-catalyzed enantioselective Friedel–Crafts reactions of indoles...
Scheme 52: CPA-catalyzed enantioselective allylation of 3-indolylmethanols.
Scheme 53: 3-Indolylmethanol-based substitution and cycloaddition reactions.
Scheme 54: CPA-catalyzed asymmetric [3 + 3] cycloaddtion reactions of 3-indolylmethanols with azomethine ylide...
Scheme 55: CPA-catalyzed three-component cascade Michael/Pictet–Spengler reactions of 3-indolylmethanols and a...
Scheme 56: Acid-promoted chemodivergent and stereoselective synthesis of diverse indole derivatives.
Scheme 57: CPA-catalyzed asymmetric formal [3 + 2] cycloadditions.
Scheme 58: CPA-catalyzed enantioselective cascade reactions for the synthesis of C7-functionlized indoles.
Scheme 59: Lewis acid-promoted Prins cyclization of 3-allyl-3-hydroxyoxindoles with aldehydes.
Scheme 60: Ga(OTf)3-catalyzed reactions of allenols and phenols.
Scheme 61: I2-catalyzed construction of pyrrolo[2.3.4-kl]acridines from enaminones and 3-indolyl-3-hydroxyoxin...
Scheme 62: CPA-catalyzed asymmetric aza-ene reaction of 3-indolylmethanols with cyclic enaminones.
Scheme 63: Asymmetric α-alkylation of aldehydes with 3-indolyl-3-hydroxyoxindoles.
Scheme 64: Organocatalytic asymmetric α-alkylation of enolizable aldehydes with 3-indolyl-3-hydroxyoxindoles a...
Bioinspired total synthesis of katsumadain A by organocatalytic enantioselective 1,4-conjugate addition
- Yongguang Wang,
- Ruiyang Bao,
- Shengdian Huang and
- Yefeng Tang
Beilstein J. Org. Chem. 2013, 9, 1601–1606, doi:10.3762/bjoc.9.182
- dramatically improve the reaction by affording 5a in a good yield (78%) and a good ee value (91%, Table 1, entry 2). Besides the catalyst B, both Jørgensen catalyst C [29] and MacMillan catalyst D [30] were also tested in this reaction, but gave inferior results (Table 1, entries 3 and 4). As to the acid
Graphical Abstract
Scheme 1: Proposed biosynthetic pathway and strategic analysis for synthesis of katsumadain A.
Scheme 2: Preliminary results of the biomimetic synthesis of katsumadain A.
Scheme 3: Total synthesis of both enantiomers of katsumadain A.
