1,2-Dichlorobenzene → HCID 117986061, compound

HRID 1055595Notes

Reaction equation

HRID 1055595 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([C:52]([OH:55])([CH3:54])[CH3:53])[CH2:11][O:12]2)C1C=CC=CC=1.ClC1C=CC=CC=1Cl>[Pd].CO.O1CCCC1>[Cl:39][C:36]1[CH:37]=[CH:38][C:33]([C@@:13]23[O:32][C@@:10]([C:52]([OH:55])([CH3:53])[CH3:54])([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

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 131736393HCID 131736393, compound

Product 1

HCID 117986061HCID 117986061, compoundYield 99.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of 2-[(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]propan-2-ol 24c (250 mg, 0.32 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL) were added o-dichlorobenzene (0.18 mL, 1.62 mmol) and 10% Pd/C (100 mg, 0.09 mmol) at room temperature. The mixture was stirred at room temperature under H2 for 4 hours and filtered. The filtrate was concentrated in vacuo and the residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=1/2 to give the title compound 24 as a white solid (160 mg, 98.7%, HPLC: 96.6%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 545 [M+HCOO]−; and 1H NMR (600 MHz, DMSO-d6) δ(ppm): 7.42 (d, 1H), 7.36 (m, 2H), 6.94 (t, 1H), 6.87 (t, 1H), 5.51 (s, 1H), 4.98 (s, 2H), 4.23 (d, 1H), 4.11 (q, 2H), 4.03 (m, 3H), 3.79 (d, 1H), 3.71 (d, 1H), 3.46 (t, 2H), 1.34 (t, 3H), 1.20 (s, 3H), 1.15 (s, 3H).

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated in vacuo
  3. customthe residue was purified by silica gel chromatography
  4. washeluted with PE/EtOAc(v/v)=1/2

Sources & evidence

ORD record
ord-a9bb005eb6d84afd8af3ce6f0bc953cc
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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