Trimethylsilyl triflate → HCID 86607072, compound

HRID 2376663Notes

Reaction equation

HRID 2376663 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=2)=[O:12])=[C:6]([NH:24][C:25]([O:27][CH2:28][CH:29]=[CH2:30])=[O:26])[CH:5]=1)(=[O:3])[CH3:2].C[Si](OS(C(F)(F)F)(=O)=O)(C)C.C([O:46][C@@H:47]1[C@@H:50]([C@H:51]([O:53][Si:54]([C:57]([CH3:60])([CH3:59])[CH3:58])([CH3:56])[CH3:55])[CH3:52])[C:49](=O)[NH:48]1)(=O)C.S([O-])(O)(=O)=O.[K+]>ClCCl.[Cl-].[Na+].O.[I-].[Zn+2].[I-].CCOCC.C(N(CC)CC)C>[CH2:28]([O:27][C:25]([NH:24][C:6]1[CH:5]=[C:4]([C:1](=[O:3])[CH2:2][C@@H:49]2[C@@H:50]([C@H:51]([O:53][Si:54]([C:57]([CH3:60])([CH3:59])[CH3:58])([CH3:55])[CH3:56])[CH3:52])[C:47](=[O:46])[NH:48]2)[CH:9]=[CH:8][C:7]=1[CH2:10][C:11]([O:13][CH2:14][C:15]1[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=1)=[O:12])=[O:26])[CH:29]=[CH2:30]

Participants

10

Reactant 4

HCID 65367Trimethylsilyl triflateHCID 516920Potassium bisulfateHCID 10935078Azetidon2×HCID 86607071HCID 86607071, compound

Product 1

HCID 86607072HCID 86607072, compoundYield 73.5%

Reagents, catalysts & solvents 5

HCID 9883512zinc(II)iodideCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To 4-nitrobenzyl (4-acetyl-2-{[(allyloxy)carbonyl]amino}phenyl)acetate (10.0 g) and triethylamine (8.2 mL) in dichloromethane (100 mL) was dropped at 0° C. trifluoromethanesulfonic acid trimethylsilyl ester (11.9 g). After detecting the production of silylenol ether by TLC, (2R,3R)-3-((1R)-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-oxo-2-azetidinyl acetate (6.98 g) and zinc iodide (4.65 g) were added thereto at 0° C. After stirring for 1 hour, further (2R,3R)-3-((1R)-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-oxo-2-azetidinyl acetate (3.0 g) was added thereto and the mixture was stirred at room temperature for 14 hours. To the reaction mixture were added a 5% aqueous potassium hydrogensulfate solution (380 mL) and saturated brine (100 mL), and the mixture was extracted with ethyl acetate (200 mL, 2×100 mL). The organic layers were combined, dried over magnesium sulfate, filtered and the solvent was removed in vacuo. The residue was purified with column chromatography (SiO2 500 g, hexane/ethyl acetate 1:1˜1:3) to give the object compound (11.4 g, 70%) as a pale amorphous.

Workup

  1. additionwere added
  2. customat 0° C
  3. stirringthe mixture was stirred at room temperature for 14 hours
  4. extractionthe mixture was extracted with ethyl acetate (200 mL, 2×100 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customthe solvent was removed in vacuo
  8. customThe residue was purified with column chromatography (SiO2 500 g, hexane/ethyl acetate 1:1˜1:3)

Sources & evidence

ORD record
ord-db5694dc86734a498fba0556d52fd932
Source dataset
uspto-grants-2008_12
Patent number
US07468364B2

Reaction notes

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