Trimethylsilyldiazomethane → HCID 69013345, compound

HRID 1854323Notes

Reaction equation

HRID 1854323 reaction equation
[O:1]=[C:2]1[C@H:7]2[CH2:8][C@H:4]([CH:5]=[CH:6]2)[N:3]1[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10].[CH3:16][Si:17]([CH:20]=[N+]=[N-])([CH3:19])[CH3:18]>CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:12]([O:11][C:9]([N:3]1[C:2](=[O:1])[C@H:7]2[CH2:8][C@@H:4]1[C@H:5]1[C@@H:6]2[CH:16]1[Si:17]([CH3:20])([CH3:19])[CH3:18])=[O:10])([CH3:15])([CH3:14])[CH3:13]

Participants

5

Reactant 2

HCID 167693TrimethylsilyldiazomethaneHCID 11830665(1R,4S)-tert-Butyl 3-oxo-2-azabicyclo[2.2.1]hept-5-ene-2-carboxylate

Product 1

HCID 69013345HCID 69013345, compoundYield 92.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolvent

Procedure

To a solution of (1R,4S)-tert-butyl 3-oxo-2-azabicyclo[2.2.1]hept-5-ene-2-carboxylate (1.3 g, 6.2 mmol) and palladium(II) acetate (0.070 g, 0.31 mmol) in Et2O (62 mL) was added trimethylsilyldiazomethane (2 M in hexanes, 3.00 mL, 11.5 mmol) drop-wise at ambient temperature over about 1 h. The mixture was stirred at ambient temperature for about 18 h and filtered through Celite®. The Celite® pad was washed with Et2O (50 mL) and the filtrate was concentrated under reduced pressure. The crude material was purified by silica gel chromatography eluting with a gradient of 0-30% EtOAc/heptane to afford (1S,2R,4R,5R)-7-oxo-3-trimethylsilanyl-6-aza-tricyclo[3.2.1.0(2,4)]octane-6-carboxylic acid tert-butyl ester (1.7 g, 92%). 1H NMR (400 MHz, DMSO-d6) δ 4.37 (s, 1H), 2.70 (s, 1H), 1.45 (m, 10H), 1.23 (t, 1H), 0.76 (t, 1H), 0.10 (s, 2H), −0.03 (s, 9H).

Workup

  1. filtrationfiltered through Celite®
  2. washThe Celite® pad was washed with Et2O (50 mL)
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customThe crude material was purified by silica gel chromatography
  5. washeluting with a gradient of 0-30% EtOAc/heptane

Sources & evidence

ORD record
ord-98e2d7b0f26c4b74ba73cd6fdbd75ac6
Source dataset
uspto-grants-2015_02
Patent number
US08962629B2

Reaction notes

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