N,N,N',N'-Tetramethylethylenediamine → HCID 44240214, compound

HRID 473388Notes

Reaction equation

HRID 473388 reaction equation
[CH:1]([Mg]Br)=[CH2:2].CN([CH2:8][CH2:9]N(C)C)C.[Si:13]([O:20][C@H:21]([CH2:30][O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])/[CH:22]=[N:23]\[S@:24]([C:26]([CH3:29])([CH3:28])[CH3:27])=[O:25])([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]>C1COCC1>[Si:32]([O:31][CH2:30][C@@H:21]([O:20][Si:13]([C:16]([CH3:19])([CH3:17])[CH3:18])([CH3:15])[CH3:14])[C@@H:22]([NH:23][S@:24]([C:26]([CH3:27])([CH3:28])[CH3:29])=[O:25])[CH:1]=[CH2:2])([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:33])[CH3:34].[Si:32]([O:31][CH2:30][C@@H:21]([O:20][Si:13]([C:16]([CH3:19])([CH3:17])[CH3:18])([CH3:15])[CH3:14])[C@H:22]([NH:23][S@:24]([C:26]([CH3:27])([CH3:28])[CH3:29])=[O:25])[CH:8]=[CH2:9])([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:33])[CH3:34]

Participants

6

Reactant 3

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 87421436HCID 87421436, compoundHCID 178418507HCID 178418507, compound

Product 2

HCID 44240080HCID 44240080, compoundYield 39%HCID 44240214HCID 44240214, compoundYield 54%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a 2.0 L round bottom flask containing vinylmagnesium bromide (92 ml, 92 mmol) was added THF (40 mL) and the mixture was allowed to stir at −78° C. for 5 min. At this time, TMEDA (23 ml, 154 mmol) was added via syringe followed by (S,Z)—N—((S)-2,3-bis(tert-butyldimethylsilyloxy)propylidene)-2-methylpropane-2-sulfinamide (13.0 g, 31 mmol) in THF. The reaction was allowed to stir at −78° C. for 4 h and then allowed to slowly warm to RT overnight. The reaction was quenched by the addition of ammonium chloride (sat, 100 ml). The aqueous layer was extracted with EtOAc, washed with brine, dried sodium sulfate, filtered and concentrated to give a crude oil that was purified by silica gel column to give (S)—N-((2S,3S)-1,2-bis(tert-butyldimethylsilyloxy)pent-4-en-3-yl)-2-methylpropane-2-sulfinamide (5.45 g, 39% yield, higher Rf) and (S)—N-((2S,3R)-1,2-bis(tert-butyldimethylsilyloxy)pent-4-en-3-yl)-2-methylpropane-2-sulfinamide (7.43 g, 54% yield, lower Rf).

Workup

  1. stirringto stir at −78° C. for 4 h
  2. temperatureto slowly warm to RT overnight
  3. customThe reaction was quenched by the addition of ammonium chloride (sat, 100 ml)
  4. extractionThe aqueous layer was extracted with EtOAc
  5. washwashed with brine, dried sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a crude oil that
  9. customwas purified by silica gel column

Sources & evidence

ORD record
ord-aa8901338c2142fe875a314b34e5a002
Source dataset
uspto-grants-2014_01
Patent number
US08633315B2

Reaction notes

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