Ammonium Chloride → (1S,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-hydroxy-6,8-dioxabicyclo[3.2.1]octane-1-carbaldehyde

HRID 1055619Notes

Reaction equation

HRID 1055619 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@:14]2([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[C:27]([CH2:32][C:33]4[CH:38]=[CH:37][C:36]([O:39][CH2:40][CH3:41])=[CH:35][CH:34]=4)[CH:26]=3)[O:24][C@@:11]([CH2:42][OH:43])([CH2:12][O:13]2)[C@@H:10]1[OH:44])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O)[O-].[Na+].[Br-].[K+].Cl[O-].[Na+].[Cl-].[NH4+]>ClCCl>[CH2:1]([O:8][C@@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@:14]2([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[C:27]([CH2:32][C:33]4[CH:34]=[CH:35][C:36]([O:39][CH2:40][CH3:41])=[CH:37][CH:38]=4)[CH:26]=3)[O:24][C@@:11]([CH:42]=[O:43])([CH2:12][O:13]2)[C@@H:10]1[OH:44])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 5

HCID 25517Ammonium ChlorideHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 118391255(1S,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octan-2-ol

Product 1

HCID 118391148(1S,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-hydroxy-6,8-dioxabicyclo[3.2.1]octane-1-carbaldehydeYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (1S,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octan-2-ol 28j (0.22 g, 0.36 mmol) in dichloromethane (20 mL) was added saturated aqueous sodium bicarbonate (0.3 g, 3.6 mmol) at room temperature. To the mixture was added potassium bromide (25.7 mg, 0.22 mmol), 2,2,6,6-tetramethylpiperidinooxy (5.6 mg, 0.04 mmol) and sodium hypochlorite (0.8 mL, 0.94 mmol, 3.14% available chlorine) in turn at 0° C. The resulting mixture was stirred at 0° C. for 10 min and adjusted with saturated aqueous ammonium chloride till pH becomes 7. The resulting mixture was extracted with dichloromethane (15 mL×2). The combined organic layers were washed with water (10 mL×2) and saturated aqueous sodium chloride (10 mL×2), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound 28k as a white solid (221 mg, 100%).

Workup

  1. extractionThe resulting mixture was extracted with dichloromethane (15 mL×2)
  2. washThe combined organic layers were washed with water (10 mL×2) and saturated aqueous sodium chloride (10 mL×2)
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-67d40941fcba410197107da4c3e40f21
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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