1,2-Dichlorobenzene → HCID 117986013, compound

HRID 1055525Notes

Reaction equation

HRID 1055525 reaction equation
[C:1](=[O:57])([O:5][CH:6]([C@:8]12[O:15][C@:12]([C:16]3[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([CH2:23][C:24]4[CH:29]=[CH:28][C:27]([O:30][CH2:31][CH3:32])=[CH:26][CH:25]=4)[CH:17]=3)([O:13][CH2:14]1)[C@H:11]([O:33]CC1C=CC=CC=1)[C@@H:10]([O:41]CC1C=CC=CC=1)[C@@H:9]2[O:49]CC1C=CC=CC=1)[CH3:7])[O:2][CH2:3][CH3:4].ClC1C=CC=CC=1Cl>[Pd].CO.O1CCCC1>[C:1](=[O:57])([O:2][CH2:3][CH3:4])[O:5][CH:6]([C@:8]12[O:15][C@:12]([C:16]3[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([CH2:23][C:24]4[CH:29]=[CH:28][C:27]([O:30][CH2:31][CH3:32])=[CH:26][CH:25]=4)[CH:17]=3)([O:13][CH2:14]1)[C@H:11]([OH:33])[C@@H:10]([OH:41])[C@@H:9]2[OH:49])[CH3:7]

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377824HCID 118377824, compound

Product 1

HCID 117986013HCID 117986013, compoundYield 80.7%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of ethyl 1-[(1R,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxy phenyl) methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]ethyl carbonate 12a (76.3 g, 0.09 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL) were added o-dichlorobenzene (0.05 mL, 0.48 mmol) and 10% Pd/C (12 mg, 0.01 mmol) at room temperature. The mixture was stirred at room temperature under H2 for 4 hours and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=1/4 to give the title compound 12 as a light yellow solid (38 mg, 60%, HPLC: 89.7%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 523.2 [M+H]+; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.40 (m, 2H), 7.29 (m, 1H), 7.09 (s, 2H), 6.83 (m, 2H), 5.59 (d, 1H), 5.13 (d, 1H), 5.02 (d, 1H), 4.93 (m, 1H), 4.14-4.02 (m, 3H), 4.02-3.92 (m, 4H), 3.55 (d, 2H), 3.47-3.37 (m, 2H), 1.31 (m, 6H), 1.19 (t, 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)=1/4

Sources & evidence

ORD record
ord-7c1f32f7518246d193e91d6c07c13c1b
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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