1,2-Dichlorobenzene → HCID 117986011, compound

HRID 1055529Notes

Reaction equation

HRID 1055529 reaction equation
[CH3:1][C:2]([CH3:58])([CH3:57])[C:3]([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:4].ClC1C=CC=CC=1Cl>[Pd].CO.O1CCCC1>[Cl:22][C:19]1[CH:20]=[CH:21][C:16]([C@@:12]23[O:15][C@@:8]([CH:6]([O:5][C:3](=[O:4])[C:2]([CH3:58])([CH3:57])[CH3:1])[CH3:7])([CH2:14][O:13]2)[C@@H:9]([OH:49])[C@H:10]([OH:41])[C@H:11]3[OH:33])=[CH:17][C:18]=1[CH2:23][C:24]1[CH:29]=[CH:28][C:27]([O:30][CH2:31][CH3:32])=[CH:26][CH:25]=1

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377815HCID 118377815, compound

Product 1

HCID 117986011HCID 117986011, compoundYield 77.6%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of 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]ethyl 2,2-dimethyl propanoate 14a (120 mg, 0.15 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL) were added o-dichlorobenzene (0.08 mL, 0.72 mmol) and 10% Pd/C (19 mg, 0.02 mmol) in turn 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)=4/1 to give the title compound 14 as a white solid (62.3 mg, 77.6%, HPLC: 85.3%). The compound was characterized by the following spectroscopic data: MS(ESI, pos. ion) m/z: 580.3[M+HCOO]−; and 1H NMR (600 MHz, DMSO-d6) δ(ppm): 7.42 (m, 2H), 7.32 (m, 1H), 7.08 (m, 2H), 6.82 (m, 2H), 5.38 (brs, 1H), 5.06 (m, 1H), 4.04 (d, 1H), 3.97 (m, 3H), 3.57 (d, 1H), 3.52 (d, 1H), 3.47 (m, 3H), 1.30 (t, 3H), 1.23 (d, 3H), 1.10 (s, 9H).

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)=4/1

Sources & evidence

ORD record
ord-3d9acb7c5c8c47c189cb0500b1513be3
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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