(Diethylamino)sulfur trifluoride → methyl (2E)-((3R,5S)-3-{[tert-butyl(diphenyl)silyl]oxy}-5-fluoro-4-methylenecyclohexylidene)acetate

HRID 388752Notes

Reaction equation

HRID 388752 reaction equation
[Si:1]([O:18][C@H:19]1[C:24](=[CH2:25])[C@H:23](O)[CH2:22]/[C:21](=[CH:27]/[C:28]([O:30][CH3:31])=[O:29])/[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(S(F)(F)[F:38])CC)C>ClCCl>[Si:1]([O:18][C@H:19]1[C:24](=[CH2:25])[C@@H:23]([F:38])[CH2:22]/[C:21](=[CH:27]/[C:28]([O:30][CH3:31])=[O:29])/[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 131730230Methyl (2z)-((3r,5r)-3-{[tert-butyl(diphenyl)silyl]oxy}-5-hydroxy-4-methylenecyclohexylidene)acetate

Product 1

HCID 131730231methyl (2E)-((3R,5S)-3-{[tert-butyl(diphenyl)silyl]oxy}-5-fluoro-4-methylenecyclohexylidene)acetate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The compound of Example 18A (600 mg, 0.23 mmol) was dissolved in 2.4 mL of dichloromethane, and the resultant solution was cooled to −78° C. (Diethylamino)sulfur trifluoride (DAST, 0.6 mL) was added; the mixture was stirred for 30 minutes, and then quenched by addition of saturated aqueous sodium bicarbonate solution. The mixture was warmed to ambient temperature; the organic phase was dried over Na2SO4. The solvents were removed in vacuo; the residue was purified by chromatography on an Analogix IntelliFlash 280™, eluting with a gradient of 5% to 7% ethyl acetate in hexanes, to give the titled compound, plus some mixed fractions.

Workup

  1. additionwas added
  2. customquenched by addition of saturated aqueous sodium bicarbonate solution
  3. dry with materialthe organic phase was dried over Na2SO4
  4. customThe solvents were removed in vacuo
  5. customthe residue was purified by chromatography on an Analogix IntelliFlash 280™
  6. washeluting with a gradient of 5% to 7% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-2d7b677769144990881525cd99d121c5
Source dataset
uspto-grants-2013_02
Patent number
US08377913B2

Reaction notes

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