2-Hydroxy-2-[(tert-butyldiphenylsilyloxy)methyl]-1-tetradecanoyloxy-4-pentene → 5-[(tert-Butyldiphenylsilyloxy)methyl]-5-[(tetradecanoyloxy)methyl]-tetrahydro-2-furanone

HRID 363496Notes

Reaction equation

HRID 363496 reaction equation
[OH:1][C:2]([CH2:23][O:24][Si:25]([C:38]([CH3:41])([CH3:40])[CH3:39])([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)([CH2:20][CH:21]=[CH2:22])[CH2:3][O:4][C:5](=[O:19])[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[Cr](Cl)([O-])(=O)=[O:43].[NH+]1C=CC=CC=1>C1COCC1.C(Cl)Cl.CCOCC>[Si:25]([O:24][CH2:23][C:2]1([CH2:3][O:4][C:5](=[O:19])[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[O:1][C:22](=[O:43])[CH2:21][CH2:20]1)([C:38]([CH3:40])([CH3:39])[CH3:41])([C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

6

Reactant 2

HCID 108409882-Hydroxy-2-[(tert-butyldiphenylsilyloxy)methyl]-1-tetradecanoyloxy-4-penteneHCID 178418287HCID 178418287, compound

Product 1

HCID 108412125-[(tert-Butyldiphenylsilyloxy)methyl]-5-[(tetradecanoyloxy)methyl]-tetrahydro-2-furanoneYield 71%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A stirred solution of 2d (1.04 g, 1.8 mmol) in dry THF (35 mL) at -78° C. was treated dropwise with a THF solution of BH3 ·SMe2 (2M, 1.8 mL) while maintained under a blanket of argon. The reaction mixture was allowed to reach room temperature during the course of 3 h and was stirred further for 12 h. Evaporation of the solvent under reduced pressure gave a residue that was dissolved in dry CH2Cl2 (100 mL) and treated with pyridinium chlorochromate (PCC, 15 g, 69.5 mmol). The dark reaction mixture was stirred at room temperature for 3 days and was diluted with dry ether (500 mL) before being filtered through a short silica gel column. The solution obtained was dried (Na2SO4) and reduced to dryness. The residue was purified by flash column chromatography over silica gel using 10% EtOAc in hexane as eluant to give 3d (0.758 g, 71%) as a pale yellow oil; IR (neat) 1785.6, 1743.5 cm-1 ; 1H NMR (CDCl3) δ 0.87 (distorted t, 3 H, CH3), 1.05 (s, 9 H, C(CH3)3), 1.25 (m, 20 H, CH3 (CH2)10CH2CH2CO); 1.55 (m, 2 H, CH3 (CH2)10CH2CH2CO), 2.00-2.40 (m, 4 H, H-4, CH3 (CH2)10CH2CH2CO), 2.60 (m, 2 H, H-3), 3.70 (AB q, J=10.8 Hz, 2 H, CH2OSi), 4.20 (AB q, J=12.0 Hz, 2 H, CH2OCO), 7.30-7.70 (m, 10 H, Ph); 13C NMR δ 14.10, 19.17, 22.67, 24.78. 25.91, 26.72, 28.87, 29.08, 29.20, 29.33, 29.41, 29.57, 29.62, 31.90, 34.03, 65.64, 66.15, 85.77, 127.88, 130.01, 132.25, 132.50, 135.52, 135.59, 173.15, 176.28. Anal. Calcd for C36H54O5Si: C,72.68; H, 9.16. Found: C,72.76; H, 9.22.

Workup

  1. temperaturewhile maintained under a blanket of argon
  2. customto reach room temperature during the course of 3 h
  3. customEvaporation of the solvent under reduced pressure
  4. customgave a residue that
  5. customThe dark reaction mixture
  6. stirringwas stirred at room temperature for 3 days
  7. filtrationbefore being filtered through a short silica gel column
  8. customThe solution obtained
  9. dry with materialwas dried (Na2SO4)
  10. customThe residue was purified by flash column chromatography over silica gel using 10% EtOAc in hexane as eluant

Sources & evidence

ORD record
ord-a7fc53647fe7457a83f147aba3a5b19b
Source dataset
uspto-grants-1999_02
Patent number
US05874464

Reaction notes

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