p-Toluenesulfonic acid monohydrate → HCID 86653960, compound

HRID 1910658Notes

Reaction equation

HRID 1910658 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:21]([O:22][C:23]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:24])[C@:20]([CH3:33])([OH:32])[C@@H:19]([CH2:34][O:35][Si](C(C)(C)C)(C)C)[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>CC#N.O.CCOC(C)=O>[CH2:1]([O:8][C@@H:9]1[C@@H:21]([O:22][C:23]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:24])[C@:20]([CH3:33])([OH:32])[C@@H:19]([CH2:34][OH:35])[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:16])([CH3:17])[CH3:15])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 131731073HCID 131731073, compound

Product 1

HCID 86653960HCID 86653960, compoundYield 96.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of 5.10 (4.7 g, 7.6 mmol) in CH3CN (30 mL) and H2O (30 mL) was added p-toluenesulfonic acid monohydrate (115 mg, 0.76 mmol). The reaction was stirred for 3 h then diluted with EtOAc and washed sequentially with saturated aqueous NaHCO3, H2O, and brine. After concentration of the organic phase in vacuo, the crude residue was purified by silica gel chromatography (50% EtOAc/petroleum ether) to afford the title compound (3.7 g, 7.3 mmol, 96%). 1H NMR (500 MHz, CDCl3): δ ppm 7.39-7.22 (m, 8H, PhH), 7.10 (d, J=7.3 Hz, 2H, PhH), 4.94, 4.67 (ABq, J=11.2 Hz, 1H each, OCH2Ph), 4.88 (d, J=9.8 Hz, 1H, H-3), 4.53 (d, J=7.8 Hz, 1H, H-1), 4.04-3.96 (m, 1H, OCHHCH2SiMe3), 3.91 (dd, J=11.7, 4.9 Hz, 1H, H-6), 3.78 (dd, J=11.7, 6.8 Hz, 1H, H-6), 3.67-3.59 (m, 1H, OCHHCH2SiMe3), 3.46 (dd, J=6.8, 5.4 Hz, 1H, H-5), 3.39 (dd, J=10.0, 7.6 Hz, 1H, H-2), 1.29 (s, 3H, Me), 1.04 (t, J=8.5 Hz, 2H, OCH2CH2SiMe3), 0.04 (s, 9H, SiMe3); 13C NMR (125 MHz, CDCl3): δ ppm 154.43, 151.15, 138.34, 129.61, 128.50, 127.81, 127.73, 126.31, 121.06, 103.64, 84.03, 79.21, 77.45, 74.92, 73.40, 68.21, 61.05, 18.73, 15.90, −1.27; HRMS calcd for C26H40NO8Si [M+NH4]+: 522.2523. found 522.2501.

Workup

  1. washwashed sequentially with saturated aqueous NaHCO3, H2O, and brine
  2. customAfter concentration of the organic phase in vacuo, the crude residue was purified by silica gel chromatography (50% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-0864a45a12b44d65b152bdf94fe63410
Source dataset
uspto-grants-2013_12
Patent number
US08604004B2

Reaction notes

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