Sodium Sulfate → HCID 117974988, compound

HRID 1776107Notes

Reaction equation

HRID 1776107 reaction equation
[CH3:1]N(C)C1C2C(=CC=CC=2N(C)C)C=CC=1.[C:17]([O:21][C:22](=[O:44])[N:23]([C@H:27]1[CH2:35][CH2:34][CH2:33][C@H:32]([CH2:36][CH2:37][CH:38]([CH3:40])[CH3:39])[C@@H:31]([OH:41])[C@H:30]([CH3:42])[O:29][C:28]1=[O:43])[CH2:24][O:25][CH3:26])([CH3:20])([CH3:19])[CH3:18].[O-]S([O-])(=O)=O.[Na+].[Na+].F[B-](F)(F)F.C[O+](C)C>C(Cl)Cl.CCOC(C)=O>[C:17]([O:21][C:22](=[O:44])[N:23]([C@H:27]1[CH2:35][CH2:34][CH2:33][C@H:32]([CH2:36][CH2:37][CH:38]([CH3:39])[CH3:40])[C@@H:31]([O:41][CH3:1])[C@H:30]([CH3:42])[O:29][C:28]1=[O:43])[CH2:24][O:25][CH3:26])([CH3:19])([CH3:18])[CH3:20]

Participants

7

Reactant 4

HCID 24436Sodium SulfateHCID 88675Proton spongeHCID 2735153Oxonium, trimethyl-, tetrafluoroborate(1-) (1:1)HCID 117974986HCID 117974986, compound

Product 1

HCID 117974988HCID 117974988, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To an oven-dried vial were added N1,N1,N8,N8-tetramethylnaphthalene-1,8-diamine (Proton Sponge®; 1.63 g, 7.60 mmol), tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-isopentyl-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate (436 mg, 1.086 mmol), anhydrous Na2SO4 (1.15 g, 8.10 mmol), and trimethyloxonium tetrafluoroborate (723 mg, 4.89 mmol) in anhydrous CH2Cl2 (11 mL) at 0° C. The reaction mixture was slowly warmed to room temperature and stirred for 5 h. The reaction mixture was diluted with EtOAc, filtered, and the filtrate was washed with water. The phases were separated and the aqueous phase was extracted with additional EtOAc, and the combined organic phases were washed with 1.0 M aqueous sodium bisulfate (NaHSO4), washed with saturated aqueous NaHCO3, dried over MgSO4, concentrated, and purified by column chromatography on SiO2 (gradient, hexanes/EtOAc) to provide the title compound as a mixture of rotamers in the form of a white solid (320 mg, 71%): IR (neat) 2934, 1747, 1705, 1454, 1366, 1296, 1170, 1080 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.97-4.70 (m, 3H), 4.60-4.47 (m, 0.5H), 4.25-4.11 (m, 0.5H), 3.49 (s, 3H), 3.40-3.28 (m, 3H), 2.97-2.86 (m, 1H), 2.17-2.01 (m, 1H), 1.79-1.42 (m, 16H), 1.42 (d, J=6.4 Hz, 3H), 1.31-1.07 (m, 3H), 0.99-0.82 (m, 7H); 13C NMR (101 MHz, CDCl3) δ 173.54, 155.56, 155.39, 86.39, 81.02, 80.98, 76.34, 75.50, 74.70, 74.43, 61.04, 58.62, 57.11, 55.45, 55.36, 43.42, 36.40, 30.67, 29.62, 28.20, 28.15, 28.09, 27.31, 27.04, 23.05, 22.12, 19.19, 18.10; HRMS-ESI (m/z) ([M]+) calcd for C22H41NO6, 415.2934; found, 415.2943.

Workup

  1. filtrationfiltered
  2. washthe filtrate was washed with water
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted with additional EtOAc
  5. washthe combined organic phases were washed with 1.0 M aqueous sodium bisulfate (NaHSO4)
  6. washwashed with saturated aqueous NaHCO3
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. custompurified by column chromatography on SiO2 (gradient, hexanes/EtOAc)

Sources & evidence

ORD record
ord-3482f2ee0a92412dbd1e4c1c0a22b0e4
Source dataset
uspto-grants-2016_02
Patent number
US09265253B2

Reaction notes

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