Sodium ethanethiolate → 5-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(2-methylallyl)tetrahydro-2H-pyran-2-yl)phenol

HRID 1713592Notes

Reaction equation

HRID 1713592 reaction equation
C([S-])C.[Na+].[CH2:5]([O:12][C@@H:13]1[C@@H:18]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:17]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@@H:16]([CH2:35][O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[O:15][C@:14]1([C:48]1[CH:53]=[C:52]([CH2:54][C:55]2[CH:60]=[CH:59][C:58]([CH2:61][CH3:62])=[CH:57][CH:56]=2)[C:51]([Cl:63])=[CH:50][C:49]=1[O:64]C)[CH2:44][C:45]([CH3:47])=[CH2:46])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>CN(C=O)C>[Cl:63][C:51]1[C:52]([CH2:54][C:55]2[CH:60]=[CH:59][C:58]([CH2:61][CH3:62])=[CH:57][CH:56]=2)=[CH:53][C:48]([C@@:14]2([CH2:44][C:45]([CH3:47])=[CH2:46])[C@H:13]([O:12][CH2:5][C:6]3[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=3)[C@@H:18]([O:19][CH2:20][C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[C@H:17]([O:27][CH2:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[C@@H:16]([CH2:35][O:36][CH2:37][C:38]3[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=3)[O:15]2)=[C:49]([OH:64])[CH:50]=1

Participants

4

Reactant 2

HCID 4459711Sodium ethanethiolateHCID 68794579HCID 68794579, compound

Product 1

HCID 687926765-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(2-methylallyl)tetrahydro-2H-pyran-2-yl)phenolYield 92%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of sodium ethanethiolate (151 mg, 1.79 mmol) and 24 (150 mg, 0.179 mmol) in DMF (3 mL) was flushed with argon and heated at 90° C. for 3 h. The reaction mixture was cooled to 0° C. A mixture of acetic acid and water (1:1, 2 mL) was added. The resulting mixture was stirred for 10 min and then concentrated to dryness. The residue was partitioned between water and dichloromethane. The organic layer was separated, dried (Na2SO4), and evaporated. The residue was purified by preparatory TLC eluting with 10% EtOAc in petroleum ether to give 25 (135 mg, 92%). LC/MS m/z 846 (M+Na).

Workup

  1. customwas flushed with argon
  2. temperatureThe reaction mixture was cooled to 0° C
  3. additionA mixture of acetic acid and water (1:1, 2 mL)
  4. additionwas added
  5. concentrationconcentrated to dryness
  6. customThe residue was partitioned between water and dichloromethane
  7. customThe organic layer was separated
  8. dry with materialdried (Na2SO4)
  9. customevaporated
  10. customThe residue was purified by preparatory TLC
  11. washeluting with 10% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-31a18911730649f9b1ca5623e997978d
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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