Pyridine → N-(t-butyldimethylsilyl)-4-(3-benzyloxycarbonyl-2-oxopropyl)-azetidin-2-one

HRID 371275Notes

Reaction equation

HRID 371275 reaction equation
N1C=CC=CC=1.[Si:7]([N:14]1[CH:17]([CH2:18][CH:19]([OH:31])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])[CH2:16][C:15]1=[O:32])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]>C(Cl)Cl.[O-2].[O-2].[O-2].[Cr+6]>[Si:7]([N:14]1[CH:17]([CH2:18][C:19](=[O:31])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])[CH2:16][C:15]1=[O:32])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]

Participants

5

Reactant 2

HCID 1049PyridineHCID 12804719N-(t-butyldimethylsilyl)-4-(3-benzyloxycarbonyl-2-hydroxypropyl)-azetidin-2-one

Product 1

HCID 12804720N-(t-butyldimethylsilyl)-4-(3-benzyloxycarbonyl-2-oxopropyl)-azetidin-2-oneYield 73.2%

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

Anhydrous CrO3 (2.274 g, 22.74 mmol) is added to a solution of anhydrous pyridine (3.597 g, 45.48 mmol) in anhydrous CH2Cl2 (60 ml). After stirring at room temperature (25° C.) for 15 mins, the reaction mixture is treated all at once with a solution of N-(t-butyldimethylsilyl)-4-(3-benzyloxycarbonyl-2-hydroxypropyl)-azetidin-2-one (1.432 g, 3.79 mmol) in anhydrous CH2Cl2 (25 ml). The resulting mixture is stirred at 25° C. for 5 mins. The CH2Cl2 layer is decanted from the dark, gummy residue which is triturated with more CH2Cl2. The combined CH2Cl2 phase is evaporated i.v. The residue is triturated with diethylether (Et2O) (100 ml) in several portions and the Et2O extracts are filtered to remove chromium salts. The ethereal filtrate is washed with 5% NaHCO3, 1N HCl, 5% NaHCO3 and brine, dried with MgSO4, filtered, and evaporated i.v. to yield N-(t-butyldimethylsilyl)-4-(3-benzyloxycarbonyl-2-oxopropyl)-azetidin-2-one (1.042 g) as a pale yellow oil: ir (neat) 5.72 (3 poorly resolved peaks), 7.59 7.98, 8.42, and 11.93 cm-1 ; nmr (CDCl3)δ 0.18 (s, 3), 0.22 (s, 3), 0.97 (s, 9), 2.53 (dd, 1), 2.63 (dd, 1), 3.13 (dd, 1), 3.28 (dd, 1), 3.47 (s,2), 3.88 (m, 1), 5.17 (s, 2), and 7.33 (s, 5); mass spectrum m/e 360, 318, and 2.76.

Workup

  1. stirringThe resulting mixture is stirred at 25° C. for 5 mins
  2. customThe CH2Cl2 layer is decanted from the dark, gummy residue which
  3. customis triturated with more CH2Cl2
  4. customThe combined CH2Cl2 phase is evaporated i.v
  5. customThe residue is triturated with diethylether (Et2O) (100 ml) in several portions
  6. filtrationthe Et2O extracts are filtered
  7. customto remove chromium salts
  8. washThe ethereal filtrate is washed with 5% NaHCO3, 1N HCl, 5% NaHCO3 and brine
  9. dry with materialdried with MgSO4
  10. filtrationfiltered
  11. customevaporated i.v

Sources & evidence

ORD record
ord-7ea22b5cbb1a4a4197ba93e357f323ad
Source dataset
uspto-grants-1985_07
Patent number
US04530841

Reaction notes

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