2-Methyl-2-butene → HCID 118377931, compound

HRID 1055518Notes

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.P(O)(O)([O-])=[O:55].[K+].CC(=CC)C.Cl([O-])=O.[Na+]>C(O)(C)(C)C.O>[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([CH2:52][OH:53])[C:50]([OH:55])=[O:51])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 35 °C

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 (1.40 g, 1.98 mmol, obtained from the synthetic method described in step 1 of example 8) in tert-butanol (10 mL) were added monopotassium phosphate (2.43 g, 17.82 mmol) and 2-methylbut-2-ene (68.88 mg, 97.02 mmol) at room temperature in turn, and then sodium chlorite (1.26 g, 13.90 mmol) and water (5 mL) were added. The mixture was stirred at 35° C. for 24 hours and quenched with 10 mL of saturated aqueous sodium bicarbonate. Tert-butanol was removed in vavuo. The resulting mixture was extracted with ethyl acetate (10 mL×3). The combined organic layers were washed with saturated aqueous sodium chloride (10 mL×2), dried over anhydrous sodium sulfate and concentrated in vacuo to give the title compound 9a as pale yellow oil (1.50 g, 100%). The crude product was used in next step without further purification.

Workup

customquenched with 10 mL of saturated aqueous sodium bicarbonate
customTert-butanol was removed in vavuo
extractionThe resulting mixture was extracted with ethyl acetate (10 mL×3)
washThe combined organic layers were washed with saturated aqueous sodium chloride (10 mL×2)
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-e68303fa459d48ec894b229b8f8290ef
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09394329B2

Reaction notes

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