1,2-Dichlorobenzene → HCID 117986005, compound

HRID 1055522Notes

Reaction equation

HRID 1055522 reaction equation
[NH2:1][CH2:2][CH:3]([C@:5]12[O:12][C@:9]([C:13]3[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([CH2:20][C:21]4[CH:26]=[CH:25][C:24]([O:27][CH2:28][CH3:29])=[CH:23][CH:22]=4)[CH:14]=3)([O:10][CH2:11]1)[C@H:8]([O:30]CC1C=CC=CC=1)[C@@H:7]([O:38]CC1C=CC=CC=1)[C@@H:6]2[O:46]CC1C=CC=CC=1)[OH:4].ClC1C=CC=CC=1Cl>[Pd].CO.O1CCCC1>[NH2:1][CH2:2][CH:3]([C@:5]12[O:12][C@:9]([C:13]3[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([CH2:20][C:21]4[CH:26]=[CH:25][C:24]([O:27][CH2:28][CH3:29])=[CH:23][CH:22]=4)[CH:14]=3)([O:10][CH2:11]1)[C@H:8]([OH:30])[C@@H:7]([OH:38])[C@@H:6]2[OH:46])[OH:4]

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377849HCID 118377849, compound

Product 1

HCID 117986005HCID 117986005, compoundYield 27.6%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of 2-amino-1-[(1R,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]ethanol 10b (205 mg, 0.28 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 25 mL) were added o-dichlorobenzene (0.16 mL, 1.42 mmol) and 10% Pd/C (32 mg, 0.03 mmol) at room temperature. The mixture was stirred at room temperature under H2 for 4 hours and filtered. The filter cake was washed with a tetrahydrofuran/methanol mixture (v/v=1/4, 10 mL×2) and the filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with EtOAc to give the title compound 10 as colorless oil (36 mg, 25.7%, HPLC: 98.0%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 466.0[M+H]+; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.73 (s, 2H), 7.42 (m, 2H), 7.31 (m, 1H), 7.09 (m, 2H), 6.82 (m, 2H), 5.52 (d, 2H), 5.02 (d, 2H), 3.95 (m, 5H), 3.72 (d, 1H), 3.61 (d, 1H), 3.48 (m, 2H), 3.14 (m, 1H), 2.69 (m, 1H), 1.28 (t, 3H).

Workup

  1. filtrationfiltered
  2. washThe filter cake was washed with a tetrahydrofuran/methanol mixture (v/v=1/4, 10 mL×2)
  3. concentrationthe filtrate was concentrated in vacuo
  4. customThe residue was purified by silica gel chromatography
  5. washeluted with EtOAc

Sources & evidence

ORD record
ord-e094bfa63aca46f084c961ba64e564a9
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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