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

HRID 8758Notes

Reaction equation

HRID 8758 reaction equation
[CH3:1][O:2][C:3]1([C:16](=[O:22])[CH2:17][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.C(N(CC)CC)C.S([N:34]=[N+:35]=[N-])(C)(=O)=O.[OH-].[Na+]>ClCCl>[CH3:1][O:2][C:3]1([C:16](=[O:22])[C:17](=[N+:34]=[N-:35])[C:18](=[O:21])[CH2:19][CH3:20])[CH2:4][CH2:5][N:6]([C:9]([O:11][C:12]([CH3:13])([CH3:15])[CH3:14])=[O:10])[CH2:7][CH2:8]1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 556271Methanesulfonyl azide2×HCID 21983976tert-Butyl 4-methoxy4-(1,3-dioxopent-1-yl)piperidine-1-carboxylate

Product 1

HCID 73857865tert-Butyl 4-methoxy-4-(2-diazo-1,3-dioxopent-1-yl)piperidine-1-carboxylateYield 70.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a solution of tert-butyl 4-methoxy-4-(1,3-dioxopent-1-yl)piperidine-1-carboxylate (0.227 g, 0.724 mmol) from Step C in dichloromethane (10 mL) was added triethylamine (0.101 mL, 0.724 mmol). Next, a solution of mesyl azide (0.087 g, 0.724 mmol) in dichloromethane (1 mL) was added. The reaction mixture was stirred for 3.5 h at room temperature. Additional mesyl azide (0.026 g, 0.217 mmol) was added. After 2 h, the reaction mixture was diluted with dichloromethane, poured into 1N sodium hydroxide solution, and extracted three times with dichloromethane. The organic layers were combined, washed with saturated sodium chloride, dried over sodium sulfite, filtered, and concentrated. The residue was purified by flash chromatography eluting with 5% ethyl acetate/dichloromethane to afford the title compound (0.174 g). MS/EI (acetonitrile/water): m/z 362 (M+Na) retention time=3.37 min.

Workup

  1. waitAfter 2 h
  2. extractionextracted three times with dichloromethane
  3. washwashed with saturated sodium chloride
  4. dry with materialdried over sodium sulfite
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography
  8. washeluting with 5% ethyl acetate/dichloromethane

Sources & evidence

ORD record
ord-18eecdd894a74a9f87c65b58f6dc5b31
Source dataset
uspto-grants-2006_08
Patent number
US07091211B2

Reaction notes

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