tert-Butyl 4-methoxy-4-(2-diazo-1,3-dioxopent-1-yl)piperidine-1-carboxylate → tert-Butyl 4-oxo-3-(1-oxoprop-1-yl)-1-oxa-8-azaspiro[4.5]decane-8-carboxylate

HRID 8759

Reaction equation

HRID 8759 reaction equation
[CH3:1][O:2][C:3]1([C:16](=[O:24])[C:17](=[N+]=[N-])[C:18](=[O:21])[CH2:19][CH3:20])[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1>ClCCl.Cl.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[O:24]=[C:16]1[C:3]2([CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]2)[O:2][CH2:1][CH:17]1[C:18](=[O:21])[CH2:19][CH3:20]

Participants

5

Reactant 1

HCID 73857865tert-Butyl 4-methoxy-4-(2-diazo-1,3-dioxopent-1-yl)piperidine-1-carboxylate

Product 1

HCID 21983892tert-Butyl 4-oxo-3-(1-oxoprop-1-yl)-1-oxa-8-azaspiro[4.5]decane-8-carboxylateYield 40.4%

Reagents, catalysts & solvents 3

HCID 152122Dirhodium tetraacetateCatalystHCID 313Hydrochloric AcidSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of rhodium acetate dimer (0.002 g, 0.005 mmol) in dichloromethane (27 mL) was heated to 81° C. A solution of tert-butyl 4-methoxy-4-(2-diazo-1,3-dioxopent-1-yl)piperidine-1-carboxylate (0.092 g, 0.270 mmol) from Step D in dichloromethane (7 mL) was added slowly dropwise over 12 min. The reaction mixture was refluxed for 45 min then poured into IN hydrochloric acid, and extracted three times with dichloromethane. The organic layers were combined, washed with saturated sodium chloride solution, dried over sodium sulfite, filtered, and concentrated. The residue was purified by flash chromatography eluting with 10% ethyl acetate/dichloromethane to afford the title compound (0.034 g).

Workup

  1. temperatureThe reaction mixture was refluxed for 45 min
  2. extractionextracted three times with dichloromethane
  3. washwashed with saturated sodium chloride solution
  4. dry with materialdried over sodium sulfite
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography
  8. washeluting with 10% ethyl acetate/dichloromethane

Sources & evidence

ORD record
ord-877888e2a7554dd4b0bc69673d1bcb3a
Source dataset
uspto-grants-2006_08
Patent number
US07091211B2

Linked notes

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