Pyridine → (3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one

HRID 1578010Notes

Reaction equation

HRID 1578010 reaction equation
N1C=CC=CC=1.[Si:7]([N:14]1[C@H:17]([CH2:18][CH:19]([OH:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[C@@H:16]([C@H:35]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])[CH3:36])[C:15]1=[O:45])([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[C@H:17]([CH2:18][C:19](=[O:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[C@@H:16]([C@H:35]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:39])[CH3:40])[CH3:36])[C:15]1=[O:45])([C:10]([CH3:12])([CH3:11])[CH3:13])([CH3:9])[CH3:8]

Participants

5

Reactant 2

HCID 1049PyridineHCID 13104637(3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-hydroxypropyl]azetidin-2-one

Product 1

HCID 13018175(3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

Anhydrous chromium trioxide (10.0 mmol) is added to a soution of anhydrous pyridine (20.0 mmol) in 30 ml of anhydrous methylene chloride. After stirring at room temperature for 15 min., the reaction mixture is treated all at once with a solution of (3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-hydroxypropyl]-azetidin-2-one (1.00 mmol) in anhydrous methylene chloride (8 ml). The resulting mixture is stirred at room temperature for 5 min. The CH2Cl2 layer is decanted from the dark, tarry residue which is triturated with more CH2Cl2. The combined CH2Cl2 phase is concentrated in vacuo. The residue is triturated with ether (100 ml) and the ether extracts are filtered. The filtrate is washed with 5% aqueous sodium bicarbonate solution, 2.5 N HCl, 5% NaHCO3 and brine, dried over magnesium sulfate and concentrated in vacuo to yield (3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1 -(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one. n.m.r. (CDCl3) δ7.85(2d-aromatic, 4), δ5.27(s,2), δ4.05(m,2), δ3.6(s,2), δ2.4-3.2(dd overlapping ABq,3), δ1.2(d,3,J=6.6), δ0.9(2s,18), δ0.22(s,6), δ0.05(s,6).

Workup

  1. stirringThe resulting mixture is stirred at room temperature for 5 min
  2. customThe CH2Cl2 layer is decanted from the dark, tarry residue which
  3. customis triturated with more CH2Cl2
  4. concentrationThe combined CH2Cl2 phase is concentrated in vacuo
  5. customThe residue is triturated with ether (100 ml)
  6. filtrationthe ether extracts are filtered
  7. washThe filtrate is washed with 5% aqueous sodium bicarbonate solution, 2.5 N HCl, 5% NaHCO3 and brine
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-725a46b2c76b49f792ff96e16c4a8b96
Source dataset
uspto-grants-1981_09
Patent number
US04290947

Reaction notes

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