1,2-Dichlorobenzene → HCID 117928572, compound

HRID 1055520Notes

Reaction equation

HRID 1055520 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([CH2:52][OH:53])[C:11]([CH3:51])([CH3:50])[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]([CH2:52][OH:53])([C:11]([CH3:51])([CH3:50])[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 117928698HCID 117928698, compound

Product 1

HCID 117928572HCID 117928572, compoundYield 39.9%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of [(1R,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-7,7-dimethyl-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 9d (50.00 mg, 0.07 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 5 mL) were added o-dichlorobenzene (0.04 mL, 0.35 mmol) and 10% Pd/C (42.40 mg, 0.04 mmol) at room temperature. The mixture was stirred at room temperature under H2 for 2 hours and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with EtOAc to give the title compound 9 as colorless oil (13.00 mg, 46.0%, HPLC: 94.04%). The compound was characterized by the following spectroscopic data: MS (ESI, neg. ion) m/z: 509 [M+HCOO]−; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.40 (m, 2H), 7.29 (dd, 1H), 7.10 (d, 2H), 6.84 (d, 2H), 5.00 (d, 1H), 4.93 (d, 1H), 4.82 (d, 1H), 4.63 (t, 1H), 3.99 (s, 2H), 3.96 (m, 1H), 3.92 (m, 1H), 3.79 (m, 1H), 3.60 (m, 1H), 3.42 (m, 2H), 3.28 (m, 1H), 1.42 (s, 3H), 1.30 (t, 3H), 0.95 (s, 3H).

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated in vacuo
  3. customThe residue was purified by silica gel chromatography
  4. washeluted with EtOAc

Sources & evidence

ORD record
ord-d329d79a8ece42168c3e7b3d1ba66f91
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

Loading…