1,2-Dichlorobenzene → HCID 86685125, compound

HRID 1913009Notes

Reaction equation

HRID 1913009 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][CH2:48][CH3:49])=[C:43]([F:50])[C:42]=4[F:51])[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][CH2:48][CH3:49])=[C:43]([F:50])[C:42]=1[F:51]

Participants

4

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 86685124HCID 86685124, compound

Product 1

HCID 86685125HCID 86685125, compoundYield 45.7%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Procedure

[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxy-2,3-difluoro-phenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 3n (550 mg, 0.74 mmol) was dissolved in 20 mL of mixed solution (THF and MeOH, v:v=1:1), followed by addition of o-dichlorobenzene (0.84 mL, 7.4 mmol) and Palladium/carbon (300 mg, 10%). The mixture was exchanged with H2 three times and stirred for 3 hours. Thereafter, the reaction mixture was filtered after a small amount of ethyl acetate was added. The filtrate was concentrated under reduced pressure and the resulting residue was purified by silica gel chromatography with elution system A to obtain the title compound (1S,2S,3S,4R,5S)-5-[4-chloro-3-[(4-ethoxy-2,3-difluoro-phenyl)methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol 3 (160 mg, white solid), yield: 45.7%. MS m/z (ESI): 472.2 [M+1]. 1H NMR (400 MHz, CDCl3): δ 7.43-7.37 (m, 3H), 6.80-6.76 (m, 2H), 4.16-4.07 (m, 5H), 3.85-3.70 (m, 2H), 3.70-3.51 (m, 4H), 1.34 (t, 3H).

Workup

  1. filtrationThereafter, the reaction mixture was filtered after a small amount of ethyl acetate
  2. additionwas added
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customthe resulting residue was purified by silica gel chromatography with elution system

Sources & evidence

ORD record
ord-070954f6e55a4c1a96424a3c4b978035
Source dataset
uspto-grants-2013_12
Patent number
US08609622B2

Reaction notes

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