N,N,N',N'-Tetramethylethylenediamine → HCID 67270120, compound

HRID 1039660Notes

Reaction equation

HRID 1039660 reaction equation
[Mg].Cl[CH2:3][C:4]1[CH:12]=[CH:11][C:7]2[O:8][CH2:9][O:10][C:6]=2[CH:5]=1.CN(CCN(C)C)C.[Si:21]([O:28][C@H:29]([CH2:38][O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:42])[CH3:41])/[CH:30]=[N:31]/[S:32]([C:34]([CH3:37])([CH3:36])[CH3:35])=[O:33])([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22]>C1COCC1.C(OCC)(=O)C.[Cl-].[NH4+].II>[O:8]1[C:7]2[CH:11]=[CH:12][C:4]([CH2:3][C@@H:30]([NH:31][S:32]([C:34]([CH3:37])([CH3:36])[CH3:35])=[O:33])[C@H:29]([O:28][Si:21]([C:24]([CH3:26])([CH3:25])[CH3:27])([CH3:23])[CH3:22])[CH2:38][O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:42])[CH3:41])=[CH:5][C:6]=2[O:10][CH2:9]1

Participants

9

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 887131,3-Benzodioxole, 5-(chloromethyl)-HCID 5462224MagnesiumHCID 87293069HCID 87293069, compound

Product 1

HCID 67270120HCID 67270120, compoundYield 63.2%

Reagents, catalysts & solvents 4

HCID 807IodineCatalystHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Procedure

To a slurry of magnesium turnings (1.09 g, 44.8 mmol) in 5 mL of THF was added iodine (0.0650 g, 0.256 mmol), followed by a solution of 5-(chloromethyl)benzo[d][1,3]dioxole (6.55 g, 38.4 mmol) in 30 mL of THF. After 1 minute, the exothermic reaction mixture was placed in an ice bath for 1 minute and then stirred at ambient temperature for 1 hour. TMEDA (7.68 ml, 51.2 mmol) was added to the reaction and the mixture was cooled to −78° C. for 5 minutes at which point a solution of (E)-N-((S)-2,3-bis(tert-butyldimethylsilyloxy)propylidene)-2-methylpropane-2-sulfinamide (5400 mg, 12.8 mmol) in 25 mL THF was added via a syring pump over 15 minutes. The reaction was allowed to warm to RT over the course of 2 hours then stirred at RT for an additional hour. The mixture was diluted with ethyl acetate (100 mL) and poured in saturated ammonium chloride (250 mL). The aqueous layer was extracted with ethyl acetate (2×250 mL) and the combined organic layers were washed with water and then brine and dried over Na2SO4. The organic colvents were filtered, concentrated under reduced pressure and the crude material was purified by silica gel to provide N-((2R,3S)-1-(benzo[d][1,3]dioxol-5-yl)-3,4-bis(tert-butyldimethylsilyloxy)butan-2-yl)-2-methylpropane-2-sulfinamide (4.51 g, 63.1% yield) as a colorless oil.

Workup

  1. waitthe exothermic reaction mixture was placed in an ice bath for 1 minute
  2. additionwas added via a syring pump over 15 minutes
  3. temperatureto warm to RT over the course of 2 hours
  4. stirringthen stirred at RT for an additional hour
  5. extractionThe aqueous layer was extracted with ethyl acetate (2×250 mL)
  6. washthe combined organic layers were washed with water
  7. dry with materialbrine and dried over Na2SO4
  8. filtrationThe organic colvents were filtered
  9. concentrationconcentrated under reduced pressure
  10. customthe crude material was purified by silica gel

Sources & evidence

ORD record
ord-fccc2f33bac74d1d802700246d187ae3
Source dataset
uspto-grants-2013_10
Patent number
US08552181B2

Reaction notes

Loading…