1,2-Dichlorobenzene → HCID 117986009, compound

HRID 1055545Notes

Reaction equation

HRID 1055545 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([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])([CH3:54])[CH3:53])([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

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377833HCID 118377833, compound

Product 1

HCID 117986009HCID 117986009, compoundYield 90.7%

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-[4-(trifluoromethoxy) phenyl]methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]propan-2-ol 16c (0.24 mg, 0.31 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 15 mL) were added o-dichlorobenzene (0.18 mL, 1.55 mmol) and 10% Pd/C (72 mg, 0.09 mmol) at room temperature. The mixture was stirred at room temperature under H2 for 30 min and filtered. The filtrate was concentrated in vacuo and the residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=1/1 to give the title compound 16 as a white solid (142 mg, 90.7%, HPLC: 97.9%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 549 [M+HCOO]−; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.47 (d, 1H), 7.42 (d, 1H), 7.36 (dd, 2.1 Hz, 1H), 7.30 (m, 4H), 5.50 (d, 1H), 5.05 (d, 1H), 5.00 (d, 1H), 4.24 (s, 1H), 4.11 (s, 2H), 4.07-3.99 (m, 1H), 3.81 (d, 1H), 3.75-3.66 (m, 1H), 3.50-3.43 (m, 1H), 3.29-3.21 (m, 1H), 1.20 (s, 3H), 1.16 (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)=1/1

Sources & evidence

ORD record
ord-b4950f36eaae40ca8782097d1665d5f5
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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