Ethanol → HCID 90177831, compound

HRID 1499311Notes

Reaction equation

HRID 1499311 reaction equation
C([O:4][C@@H:5]1[C@@H:10]([O:11]C(=O)C)[C@H:9]([O:15]C(=O)C)[C@@H:8]([S:19][CH3:20])[O:7][C@H:6]1[C:21]1[CH:26]=[CH:25][C:24]([CH3:27])=[C:23]([CH2:28][C:29]2[CH:34]=[CH:33][C:32]([OH:35])=[CH:31][CH:30]=2)[CH:22]=1)(=O)C.C(N(CC)CC)C.C1[O:45][CH:44]1CO.[CH3:48][CH2:49][OH:50]>CCOC(C)=O>[OH:50][CH:49]([CH2:44][OH:45])[CH2:48][O:35][C:32]1[CH:33]=[CH:34][C:29]([CH2:28][C:23]2[CH:22]=[C:21]([C@H:6]3[C@H:5]([OH:4])[C@@H:10]([OH:11])[C@H:9]([OH:15])[C@@H:8]([S:19][CH3:20])[O:7]3)[CH:26]=[CH:25][C:24]=2[CH3:27])=[CH:30][CH:31]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 8471Triethylamine2×HCID 11164Glycidol2×HCID 90177023HCID 90177023, compound

Product 1

HCID 90177831HCID 90177831, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (2S,3S,4R,5S,6R)-2-(3-(4-hydroxybenzyl)-4-methylphenyl)-6-(methylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (37, 50 mg, 0.10 mmol) in EtOH (1 mL) under nitrogen was added triethylamine (1.4 μL, 0.010 mmol) and glycidol (10 μL, 0.15 mmol). The reaction was heated at 80° C. overnight, then recharged with triethylamine and glycidol and heated at 90° C. for 5 hours. The reaction was cooled to room temperature, diluted with EtOAc, washed with saturated aqueous NaHCO3 and brine (with back extraction), dried over MgSO4, filtered, and concentrated under vacuum. The material was purified twice by prep HPLC (C18 30×100 mm column, 20-60% CH3CN/10 mM aqueous ammonium formate, 45 mL/min) and lyophilized to provide diol 53 as a white solid (12 mg, 27% yield). 1H NMR (400 MHz, MeOH-d4) δ ppm 7.10-7.19 (m, 3 H), 7.05 (d, J=8.8 Hz, 2 H), 6.81-6.88 (m, 2 H), 4.39 (d, J=9.3 Hz, 1 H), 4.12 (d, J=9.1 Hz, 1 H), 3.89-4.05 (m, 5 H), 3.59-3.71 (m, 2 H), 3.35-3.49 (m, 3 H), 2.20 (s, 3H), 2.14 (s, 3 H); MS (ES+) [M+NH4]+=468.

Workup

  1. temperatureheated at 90° C. for 5 hours
  2. temperatureThe reaction was cooled to room temperature
  3. washwashed with saturated aqueous NaHCO3 and brine (with back extraction)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe material was purified twice by prep HPLC (C18 30×100 mm column, 20-60% CH3CN/10 mM aqueous ammonium formate, 45 mL/min) and

Sources & evidence

ORD record
ord-9380a0a279ba4454ab1a588252e9556f
Source dataset
uspto-grants-2015_12
Patent number
US09200025B2

Reaction notes

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