(2R,3S,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-(hydroxymethyl)-6-methoxy-tetrahydropyran-2-carbaldehyde → HCID 118377802, compound

HRID 1055515Notes

Reaction equation

HRID 1055515 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@:12]([C:33]2[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]3[CH:46]=[CH:45][C:44]([O:47][CH2:48][CH3:49])=[CH:43][CH:42]=3)[CH:34]=2)([O:31][CH3:32])[O:11][C@@:10]1([CH2:52][OH:53])[CH:50]=[O:51])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:54][Mg]Br>O1CCCC1>[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@:12]([C:33]2[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]3[CH:42]=[CH:43][C:44]([O:47][CH2:48][CH3:49])=[CH:45][CH:46]=3)[CH:34]=2)([O:31][CH3:32])[O:11][C@:10]1([CH:52]([OH:53])[CH3:54])[CH2:50][OH:51])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 118377812(2R,3S,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-2-(hydroxymethyl)-6-methoxy-tetrahydropyran-2-carbaldehydeHCID 178418573HCID 178418573, compound

Product 1

HCID 118377802HCID 118377802, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2R,3S,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxyphenyl) methyl]phenyl]-2-(hydroxymethyl)-6-methoxy-tetrahydropyran-2-carbaldehyde 8a (1.38 g, 1.88 mmol) in tetrahydrofuran (30 mL) was added dropwise methylmagnesium bromide (1.9 mL, 5.63 mL) at room temperature. The mixture was stirred at room temperature for 45 min under N2 and quenched with 10 mL of saturated aqueous ammonium chloride. Most of the solvent of the mixture was removed in vacuo. The resulting mixture was extracted with ethyl acetate (10 mL×2). The combined organic layers were washed with saturated aqueous sodium chloride (5 mL×2), dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=8/1 to give the title compound 8b as colourless oil (414 mg, 30.0%). The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, DMSO-d6) δ (ppm): 7.55 (m, 1H), 7.46 (d, 1H), 7.40 (d, 1H), 7.35-7.30 (m, 5H), 7.30-7.23 (m, 8H), 7.00 (m, 4H), 6.74 (d, 2H), 5.03 (t, 1H), 4.72 (m, 4H), 4.53 (d, 1H), 4.49 (d, 1H), 4.42 (d, 1H), 4.18 (m, 2H), 4.05 (d, 1H), 3.94 (m, 2H), 3.89 (d, 1H), 3.85-3.77 (m, 2H), 3.73 (m, 1H), 3.43 (d, 1H), 2.92 (s, 3H), 1.28 (t, 3H), 1.23 (d, 3H).

Workup

  1. customquenched with 10 mL of saturated aqueous ammonium chloride
  2. customMost of the solvent of the mixture was removed in vacuo
  3. extractionThe resulting mixture was extracted with ethyl acetate (10 mL×2)
  4. washThe combined organic layers were washed with saturated aqueous sodium chloride (5 mL×2)
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography
  8. washeluted with PE/EtOAc(v/v)=8/1

Sources & evidence

ORD record
ord-5cb25d65865f4f5897bcd0f4f4219bd2
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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