Triphenyl phosphite → (S)-methyl 6-oxo-6,6a,7,8,9,10-hexahydro-5H-dipyrido[1,2-a:3',2'-e]pyrazine-3-carboxylate

HRID 2097824Notes

Reaction equation

HRID 2097824 reaction equation
C[O:2][C:3]([C@@H:5]1[CH2:10][CH2:9][CH2:8][CH2:7][N:6]1[C:11]1[C:20]([N+:21]([O-])=O)=[CH:19][C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:13][N:12]=1)=O.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.[H][H]>ClCCl.N.O[V](=O)=O.[Pt]>[O:2]=[C:3]1[NH:21][C:20]2[CH:19]=[C:14]([C:15]([O:17][CH3:18])=[O:16])[CH:13]=[N:12][C:11]=2[N:6]2[CH2:7][CH2:8][CH2:9][CH2:10][C@@H:5]12

Participants

7

Reactant 3

HCID 7540Triphenyl phosphiteHCID 58324510(S)-methyl 6-(2-(methoxycarbonyl)piperidin-1-yl)-5-nitronicotinateHCID 178418361HCID 178418361, compound

Product 1

HCID 58324495(S)-methyl 6-oxo-6,6a,7,8,9,10-hexahydro-5H-dipyrido[1,2-a:3',2'-e]pyrazine-3-carboxylateYield 89%

Reagents, catalysts & solvents 3

HCID 23939PlatinumCatalystHCID 62684Ammonium metavanadate [UN2859] [Poison]CatalystHCID 6344DichloromethaneSolvent2×

Procedure

In a bomb hydroginator, (S)-methyl 6-(2-(methoxycarbonyl)piperidin-1-yl)-5-nitronicotinate (1.95 g, 6.03 mmol), triphenyl phosphite (0.019 ml, 0.060 mmol), ammonium vanadate (0.056 g, 0.483 mmol) and platinum (5% on carbon, 0.235 g, 0.060 mmol) were mixed in dichloromethane (Volume: 30.2 ml) to give a suspension. The bomb was sealed and pressurized to 110 psi with hydrogen gas. The reaction was stirred at 110 psi 16 h, depressurized, diluted with DCM (100 mL) and refluxed 10 minutes. The hot mixture was filtered through celite and washed with DCM (50 mL). The filtrate was concentrated in vacuo to yield 1.4 g (89%) of the product as a white solid and used without further purification. [M+H] calc'd for C, 13; H, 15; N, 3O, 3, 262; found, 262.

Workup

  1. customto give a suspension
  2. customThe bomb was sealed
  3. temperaturerefluxed 10 minutes
  4. filtrationThe hot mixture was filtered through celite
  5. washwashed with DCM (50 mL)
  6. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-ecbcaa06be8a4fba8870dd540570f79b
Source dataset
uspto-grants-2013_05
Patent number
US08450323B2

Reaction notes

Loading…