2,6-Lutidine → Ethyl 2-methyl-2-(methylsulfonyl)-5-oxopentanoate

HRID 404214Notes

Reaction equation

HRID 404214 reaction equation
CC1C=CC=C(C)N=1.I([O-])(=O)(=O)=[O:10].[Na+].[CH3:15][C:16]([S:26]([CH3:29])(=[O:28])=[O:27])([CH2:22][CH2:23][CH:24]=C)[C:17]([O:19][CH2:20][CH3:21])=[O:18]>O1CCOCC1.O.[Os](=O)(=O)(=O)=O>[CH3:15][C:16]([S:26]([CH3:29])(=[O:28])=[O:27])([CH2:22][CH2:23][CH:24]=[O:10])[C:17]([O:19][CH2:20][CH3:21])=[O:18]

Participants

6

Reactant 3

HCID 79372,6-LutidineHCID 23667635Sodium periodateHCID 86709147Ethyl 2-methyl-2-(methylsulfonyl)hex-5-enoate

Product 1

HCID 77985697Ethyl 2-methyl-2-(methylsulfonyl)-5-oxopentanoateYield 100.9%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Procedure

2,6-Dimethylpyridine (6.1 mL, 52.9 mmol, 2.0 equiv), osmium tetroxide (2.5% w/v solution in tert-butyl alcohol, 6.6 mL, 0.53 mmol, 0.02 equiv), and sodium periodate (23.1 g, 106 mmol 4.0 equiv) were added sequentially to a solution of ethyl 2-methyl-2-(methylsulfonyl)hex-5-enoate (6.2 g, 26.0 mmol, 1.0 equiv) in 1,4-dioxane-water (3:1, 0.27 L) at room temperature. After vigorously stirring overnight (approx. 18 h), the reaction was partitioned between dichloromethane (0.2 L) and water (0.2 L). The aqueous phase was extracted with dichloromethane (0.2 L). The combined organic phases were washed with brine (30 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to provide the title compound as an oil (6.2 g). MS (GCMS) m/z 237 (M+1). 1H NMR (400 MHz, CHLOROFORM-d) δ1.34 (t, J=7.22 Hz, 3H) 1.63 (s, 3H) 2.21-2.39 (m, 1H) 2.56 (s, 2H) 2.65-2.81 (m, 1H) 3.05-3.17 (m, 3H) 4.30 (q, J=7.15 Hz, 2H) 9.79 (s, 1H).

Workup

  1. customthe reaction was partitioned between dichloromethane (0.2 L) and water (0.2 L)
  2. extractionThe aqueous phase was extracted with dichloromethane (0.2 L)
  3. washThe combined organic phases were washed with brine (30 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a10b351450cc4bc69255145a254427ab
Source dataset
uspto-grants-2014_06
Patent number
US08748466B2

Reaction notes

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