HCID 117928482, compound → 1-[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octane-1-yl]propan-1-ol

HRID 1055506Notes

Reaction equation

HRID 1055506 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=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([CH:50]=[O:51])[CH2:11][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:52]([Mg]Br)[CH3:53]>O1CCCC1>[CH2:1]([O:8][C@H:9]1[C@H:15]([O:16][CH2:17][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:42]=[CH:43][C:44]([O:47][CH2:48][CH3:49])=[CH:45][CH:46]=4)[CH:34]=3)[O:32][C@:10]1([CH:50]([OH:51])[CH2:52][CH3:53])[CH2:11][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 117928482HCID 117928482, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 1183777931-[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octane-1-yl]propan-1-olYield 16%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octane-1-carbaldehyde 1k (0.3 g, 0.43 mmol, obtained from the synthetic method described in step 10 of example 1) in anhydrous tetrahydrofuran (10 mL) was added dropwise ethylmagnesium bromide (1.7 mL, 1.7 mmol, 1M) at 0° C. The mixture was stirred at room temperature for 16 hours, quenched with 2 mL of saturated aqueous ammonium chloride, and extracted with dichloromethane (20 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)=10/1 to give the title compound 3a as colorless oil (48 mg, 16.0%). The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, CDCl3) δ(ppm): 7.40 (m, 1H), 7.31 (m, 10H), 7.18 (m, 5H), 7.07 (m, 2H), 6.90 (m, 2H), 6.75 (m, 2H), 4.93 (m, 2H), 4.77 (m, 2H), 4.29 (d, 1H), 4.21 (d, 1H), 4.03 (m, 3H), 3.96 (m, 4H), 3.81 (m, 1H), 3.65 (m, 2H), 2.23 (d, 1H), 1.51 (m, 2H), 1.38 (t, 3H), 0.93 (t, 3H).

Workup

  1. customquenched with 2 mL of saturated aqueous ammonium chloride
  2. extractionextracted with dichloromethane (20 mL×2)
  3. washThe combined organic layers were washed with saturated aqueous sodium chloride (5 mL×2)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel chromatography
  7. washeluted with PE/EtOAc(v/v)=10/1

Sources & evidence

ORD record
ord-c0b6a0b20cb64084af1189752ba63afe
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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