1,2-Dichlorobenzene → (1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(trifluoromethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo-[3.2.1]octane-2,3,4-triol

HRID 1913045Notes

Reaction equation

HRID 1913045 reaction equation
C([O:8][C@H:9]1[C@H:15]([O:16]CC2C=CC=CC=2)[C@@H:14]([O:24]CC2C=CC=CC=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:46]=[CH:45][C:44]([O:47][C:48]([F:51])([F:50])[F:49])=[CH:43][CH:42]=4)[CH:34]=3)[O:32][C@@:10]1([CH2:52][OH:53])[CH2:11][O:12]2)C1C=CC=CC=1.ClC1C=CC=CC=1Cl>[Pd]>[Cl:39][C:36]1[CH:37]=[CH:38][C:33]([C@@:13]23[O:32][C@@:10]([CH2:52][OH:53])([CH2:11][O:12]2)[C@@H:9]([OH:8])[C@H:15]([OH:16])[C@H:14]3[OH:24])=[CH:34][C:35]=1[CH2:40][C:41]1[CH:46]=[CH:45][C:44]([O:47][C:48]([F:50])([F:49])[F:51])=[CH:43][CH:42]=1

Participants

4

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 86685144[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[[4-(trifluoromethoxy)phenyl]methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol

Product 1

HCID 86685145(1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(trifluoromethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo-[3.2.1]octane-2,3,4-triolYield 86%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Procedure

[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[[4-(trifluoromethoxy)phenyl]methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 6r (150 mg, 0.20 mmol) was dissolved in 10 mL of mixed solution (THF and MeOH, v:v=1:1), followed by addition of o-dichlorobenzene (0.23 mL, 2 mmol) and Palladium/carbon (60 mg, 10%). The mixture was exchanged with H2 three times and stirred for 1 hour. Thereafter, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure and the resulting residue was purified by silica gel chromatography with elution system E to obtain the title compound (1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(trifluoromethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo-[3.2.1]octane-2,3,4-triol 6 (82 mg, white solid), yield: 86.0%. MS m/z (ESI): 477.1 [M+1]; 1H NMR (400 MHz, CD3OD): δ 7.54 (d, 1H), 7.46-7.39 (m, 2H), 7.30 (d, 2H), 7.17 (d, 2H), 4.17 (d, 3H), 3.86 (d, 1H), 3.80 (d, 1H), 3.72-3.68 (m, 2H), 3.62 (dd, 1H), 3.58 (d, 1H).

Workup

  1. filtrationThereafter, the reaction mixture was filtered
  2. concentrationThe filtrate was concentrated under reduced pressure
  3. customthe resulting residue was purified by silica gel chromatography with elution system E

Sources & evidence

ORD record
ord-7cb9f0630bcb4f84a8a0bae704638211
Source dataset
uspto-grants-2013_12
Patent number
US08609622B2

Reaction notes

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