Dimethyl Sulfoxide → benzhydryl (2S,3R,5R)-3-formyl-3-methyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate

HRID 263741Notes

Reaction equation

HRID 263741 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C@:13]1([CH3:37])[S:19][C@H:18]2[N:15]([C:16](=[O:20])[CH2:17]2)[C@H:14]1[C:21]([O:23][CH:24]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22].C(N(CC)CC)C>ClCCl>[CH:12]([C@:13]1([CH3:37])[S:19][C@H:18]2[N:15]([C:16](=[O:20])[CH2:17]2)[C@H:14]1[C:21]([O:23][CH:24]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)=[O:22])=[O:11]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10786198benzhydryl (2S,3R,5R)-3-hydroxymethyl-3-methyl-7-oxo-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylate

Product 1

HCID 10762402benzhydryl (2S,3R,5R)-3-formyl-3-methyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-60 °C

Procedure

100 ml of dichloromethane were treated with 0.84 ml (9.6 mmol) of oxalyl chloride under argon and cooled to -60° C. Thereto there were added dropwise 0.73 ml (10.25 mmol) of DMSO, followed by 2.5 g (6.52 mmol) of benzhydryl (2S,3R,5R)-3-hydroxymethyl-3-methyl-7-oxo-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylate dissolved in 100 ml of dichloromethane. The mixture was stirred at the same temperature for 3 hours and then 3.2 ml (23.0 mmol) of triethylamine were added. The cooling bath was removed and the mixture was left to warm to room temperature. The orange solution was poured into 1000 ml of 0.2N hydrochloric acid and the aqueous phase was extracted twice with dichloromethane. The organic phases were washed with water and saturated, aqueous sodium chloride solution, dried over sodium sulfate, filtered and concentrated on a rotary evaporator. The thus-obtained product (2.50 g, 100%) can be processed without further purification or can be recrystallized from diethyl ether. Yield: 2.00 g (80%) of white crystal powder; m.p. 111.8°-112.8° C. IR(KBr): 2720, 1788, 1743, 1718 cm-1MS: (M--CH2CO) 339 1H-NMR (250 MHz, CDCl3): δ[ppm]=1.26(s,3H), 3.06(dd,1H,J=16.2Hz, 2Hz, 6-H), 3.54(dd,1H,J=16.2Hz, 4Hz,6-H), 5.34(s,1H,2-H), 5.42(dd,1H,J=2Hz, 4Hz,5-H), 6.95(s,1H,CHPh2), 7.30-7.38 (m,10H,Ph), 9.20(s,1H).

Workup

  1. customThe cooling bath was removed
  2. waitthe mixture was left
  3. temperatureto warm to room temperature
  4. additionThe orange solution was poured into 1000 ml of 0.2N hydrochloric acid
  5. extractionthe aqueous phase was extracted twice with dichloromethane
  6. washThe organic phases were washed with water
  7. dry with materialsaturated, aqueous sodium chloride solution, dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated on a rotary evaporator
  10. customThe thus-obtained product (2.50 g, 100%) can be processed without further purification
  11. customcan be recrystallized from diethyl ether

Sources & evidence

ORD record
ord-357c6cb9bd2e4a879f4b3cbc14aa7650
Source dataset
uspto-grants-1997_07
Patent number
US05644053

Reaction notes

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