Triacetoxyperiodinane → (1R,3R,4R,5S)-3,4-dibenzyloxy-1-[(tert-butyl(dimethyl)silyl)oxymethyl]-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-2-one

HRID 1055614Notes

Reaction equation

HRID 1055614 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][O:43][Si:44]([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45])([CH2:12][O:13]2)[C@H:10]1[OH:51])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[Na]>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: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][O:43][Si:44]([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45])([CH2:12][O:13]2)[C:10]1=[O:51])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 5360545SodiumHCID 131736403(1R,2S,3S,4R,5S)-3,4-dibenzyloxy-1-[(tert-butyl(dimethyl)silyl)oxymethyl]-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-2-ol

Product 1

HCID 131736404(1R,3R,4R,5S)-3,4-dibenzyloxy-1-[(tert-butyl(dimethyl)silyl)oxymethyl]-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-2-oneYield 100.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (1R,2S,3S,4R,5S)-3,4-dibenzyloxy-1-[(tert-butyl(dimethyl) silyl)oxymethyl]-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-2-ol 28e (15.9 g, 21.7 mmol) in dichloromethane (40 mL) was added Dess-Martin periodinane (18.4 g, 43.5 mmol) at 0° C. The mixture was stirred at 0° C. for 3 hours and adjusted with saturated aqueous sodium bicarnonate till pH becomes 7. The resulting mixture was extracted with dichloromethane (100 mL×2). The combined organic phases were washed with saturated aqueous sodium chloride (100 mL×2), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound 28f as colorless oil (15.9 g, 100%). The crude product was used for next step without further purification.

Workup

  1. extractionThe resulting mixture was extracted with dichloromethane (100 mL×2)
  2. washThe combined organic phases were washed with saturated aqueous sodium chloride (100 mL×2)
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-41201189fa4346afad46292371baed82
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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