Methane, tris(methylthio)- → (4S)-1-(t-butyldimethylsilyl)-4-(2,2,2-tri(methylthio)ethyl)azetidin-2-one

HRID 1105515Notes

Reaction equation

HRID 1105515 reaction equation
C([Li])CCC.[CH3:6][S:7][CH:8]([S:11][CH3:12])[S:9][CH3:10].[Si:13]([N:20]1[C@H:23]([CH2:24]I)[CH2:22][C:21]1=[O:26])([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]>C1COCC1>[Si:13]([N:20]1[C@H:23]([CH2:24][C:8]([S:11][CH3:12])([S:9][CH3:10])[S:7][CH3:6])[CH2:22][C:21]1=[O:26])([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]

Participants

5

Reactant 3

HCID 138491Methane, tris(methylthio)-HCID 12944335(4S)-1-(t-butyldimethylsilyl)-4-iodomethyl-azetidin-2-oneHCID 178418339Butyllithium

Product 1

HCID 13003464(4S)-1-(t-butyldimethylsilyl)-4-(2,2,2-tri(methylthio)ethyl)azetidin-2-oneYield 82%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

n-Butyllithium (19.4 ml of 2.5 M hexane solution, 48.5 mmol) is added slowly by syringe to a solution of tri(methylthio)methane (7.47 g, 48.5 mmol) in 150 ml of freshly distilled THF at -78° C. The resulting solution is stirred at -78° C. for 30 min. prior to the addition of a solution of (4S)-1-(tert-butyldimethylsilyl)-4-iodomethylazetidin-2-one (15.0 g, 46.15 mmol) in 50 ml of THF. This solution is stirred at -78° C. for 30 min., then quenched by addition of saturated aqueous ammonium chloride solution. The reaction mixture is allowed to warm to room temperature, then poured into ether (250 ml), washed with water (2×100 ml) brine (100 ml) and dried over magnesium sulfate. Removal of solvents in vacuo gives an oil which is crystallized from petroleum ether to give 13.3 g (82%) of (4S)-1-(t-butyldimethylsilyl)-4-(2,2,2-tri(methylthio)ethyl)azetidin-2-one as colorless prisms. m.p. 61°-62° C. IR(CHCl3, CM-1) 2918, 2850, 1730; n.m.r. (CDCl3) δ 4.0(m,l), δ 3.35(dd,l,J=5.5,16), δ 2,83 (dd,l,J=3,16) δ 2,5(ABq,2) δ 2,15(s, 9), δ 0.98(s,9), δ0.25(s,6).

Workup

  1. stirringThis solution is stirred at -78° C. for 30 min.
  2. customquenched by addition of saturated aqueous ammonium chloride solution
  3. temperatureto warm to room temperature
  4. additionpoured into ether (250 ml)
  5. washwashed with water (2×100 ml) brine (100 ml)
  6. dry with materialdried over magnesium sulfate
  7. customRemoval of solvents in vacuo
  8. customgives an oil which
  9. customis crystallized from petroleum ether

Sources & evidence

ORD record
ord-f0d5a43d7ee8431daa0e37776616f040
Source dataset
uspto-grants-1982_01
Patent number
US04309346

Reaction notes

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