Hydrogen Peroxide → 5-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(3-hydroxypropyl)tetrahydro-2H-pyran-2-yl)phenol

HRID 1713599Notes

Reaction equation

HRID 1713599 reaction equation
[CH2:1]([C@:4]1([C:43]2[CH:48]=[C:47]([CH2:49][C:50]3[CH:55]=[CH:54][C:53]([CH2:56][CH3:57])=[CH:52][CH:51]=3)[C:46]([Cl:58])=[CH:45][C:44]=2[OH:59])[C@H:9]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@@H:8]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@H:7]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:6]([CH2:34][O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[O:5]1)[CH:2]=[CH2:3].B1C2CCCC1CCC2.[OH-:69].[Na+].OO>C1COCC1.O>[Cl:58][C:46]1[C:47]([CH2:49][C:50]2[CH:51]=[CH:52][C:53]([CH2:56][CH3:57])=[CH:54][CH:55]=2)=[CH:48][C:43]([C@@:4]2([CH2:1][CH2:2][CH2:3][OH:69])[C@H:9]([O:10][CH2:11][C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C@@H:8]([O:18][CH2:19][C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[C@H:7]([O:26][CH2:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C@@H:6]([CH2:34][O:35][CH2:36][C:37]3[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=3)[O:5]2)=[C:44]([OH:59])[CH:45]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 687951322-((2S,3R,4S,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran-2-yl)-5-chloro-4-(4-ethylbenzyl)phenol

Product 1

HCID 687917355-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(3-hydroxypropyl)tetrahydro-2H-pyran-2-yl)phenolYield 99%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of 34 (200 mg, 0.247 mmol) in dry THF (4 mL) was added 9-BBN in THF (2.0 mL, 0.5 M, 4.1 equiv). The resulting mixture was stirred at ambient temperature for 4 hours and then cooled 0° C. Water (2.5 mL), 1 M aqueous NaOH (0.8 mL) and 30% H2O2 (0.25 mL) were added at 0° C. The mixture was stirred for 1 hour at ambient temperature and 16 hours at 60° C. in a sealed vial. After cooling, the mixture was partitioned between water and EtOAc. The organic layer was dried (MgSO4), filtered and evaporated. The residue was purified using preparatory TLC eluting with 18% EtOAc in petroleum ether to give 35 (200 mg, 99% yield). LCMS m/z 828 (M+H), 850 (M+Na).

Workup

  1. temperaturecooled 0° C
  2. stirringThe mixture was stirred for 1 hour at ambient temperature and 16 hours at 60° C. in a sealed vial
  3. temperatureAfter cooling
  4. customthe mixture was partitioned between water and EtOAc
  5. dry with materialThe organic layer was dried (MgSO4)
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified
  9. washeluting with 18% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-305e8c1f936544a791e01c4f49d4c420
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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