1,2-Dichlorobenzene → HCID 117985965, compound

HRID 1055505Notes

Reaction equation

HRID 1055505 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])=[CH:43][CH:42]=4)[CH:34]=3)[O:32][C@@:10]1([C:50]([OH:53])([CH3:52])[CH3:51])[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:50]([OH:53])([CH3:52])[CH3:51])([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:42]=[CH:43][C:44]([O:47][CH2:48][CH3:49])=[CH:45][CH:46]=1

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 122610458HCID 122610458, compound

Product 1

HCID 117985965HCID 117985965, compoundYield 92.2%

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-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]propan-2-ol 2c (155 mg, 0.21 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 5 mL) were added o-dichlorobenzene (155 mg, 1.06 mmol) and 10% Pd/C (22 mg, 0.02 mmol) in turn at room temperature. The mixture was stirred at room temperature under H2 for 1 hour and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=1/2 to give the title compound 2 as a white solid (90 mg, 91.8%, HPLC: 96.8%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 509[M+HCOO]−; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.35 (s, 2H), 7.30 (dd, 1H), 7.08 (d, 2H), 6.81 (d, 2H), 5.46 (t, 1H), 5.01 (d, 1H), 4.95 (d, 1H), 4.21 (s, 1H), 3.95 (d, 5H), 3.78 (d, 1H), 3.68 (dd, 1H), 3.43 (dd, 1H), 3.35 (m, 1H), 1.28 (t, 3H), 1.18 (s, 3H), 1.13 (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-e89df480c2a34d0b9daed552b63a47fc
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

Loading…