1,2-Dichlorobenzene → HCID 117985966, compound

HRID 1055512Notes

Reaction equation

HRID 1055512 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]1([OH:53])[CH2:52][CH2:51]1)[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]4([OH:53])[CH2:51][CH2:52]4)([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][CH2:48][CH3:49])=[CH:43][CH:42]=1

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 118377866HCID 118377866, compound

Product 1

HCID 117985966HCID 117985966, compoundYield 51.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of 1-[(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]cyclopropanol 6a (75 mg, 0.1 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 5 mL) were added o-dichlorobenzene (74.97 mg, 0.51 mmol) and 10% Pd/C (15 mg, 0.01 mmol) in turn. The mixture was stirred at room temperature under H2 for 4 hours and filtered. The filter cake was washed with a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL×2). The combined filtrates were concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=1/4 to give the title compound 6 as colourless oil (24 mg, 50.0%, HPLC: 83.3%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 463.1[M+H]+; and 1H NMR (400 MHz, DMSO-d6) δ (ppm): 7.38 (m, 2H), 7.29 (m, 1H), 7.10 (m, 2H), 6.84 (m, 2H), 5.27 (s, 1H), 5.19 (d, 1H), 5.02 (d, 1H), 4.95 (d, 1H), 4.06 (m, 1H), 3.99 (m, 3H), 3.96 (m, 1H), 3.80 (t, 1H), 3.41 (m, 2H), 3.29 (m, 1H), 1.31 (t, 3H), 0.55 (m, 4H).

Workup

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

Sources & evidence

ORD record
ord-db60766ca4c3455d84e95ec567a263d5
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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