Triphenyl phosphite → methyl 6-oxo-6,7,7a,8,9,10-hexahydro-5H-pyrido[3,2-b]pyrrolo[1,2-d][1,4]diazepine-3-carboxylate

HRID 1644988Notes

Reaction equation

HRID 1644988 reaction equation
C([O:5][C:6](=O)[CH2:7][CH:8]1[CH2:12][CH2:11][CH2:10][N:9]1[C:13]1[C:22]([N+:23]([O-])=O)=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][N:14]=1)(C)(C)C.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1>ClCCl.[NH4+].[O-][V](=O)=O.[Pt]>[O:5]=[C:6]1[NH:23][C:22]2[CH:21]=[C:16]([C:17]([O:19][CH3:20])=[O:18])[CH:15]=[N:14][C:13]=2[N:9]2[CH2:10][CH2:11][CH2:12][CH:8]2[CH2:7]1

Participants

6

Reactant 2

HCID 7540Triphenyl phosphiteHCID 58324476HCID 58324476, compound

Product 1

HCID 58324492methyl 6-oxo-6,7,7a,8,9,10-hexahydro-5H-pyrido[3,2-b]pyrrolo[1,2-d][1,4]diazepine-3-carboxylateYield 72.4%

Reagents, catalysts & solvents 3

HCID 23939PlatinumCatalystHCID 516859Ammonium metavanadateCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

Methyl 6-(2-(2-tert-butoxy-2-oxoethyl)pyrrolidin-1-yl)-5-nitronicotinate (1.79 g, 4.90 mmol) was dissolved in dichloromethane (Volume: 24.49 ml) and to this solution was added triphenyl phosphite (0.015 g, 0.049 mmol), ammonium metavanadate (0.034 g, 0.294 mmol) and Pt/C (5% wt.) (0.191 g, 0.049 mmol). The reaction mixture was hydrogenated at 100 psi at 25° C. for 3 h. The reaction mixture was filtered through a short plug of celite and the plug and precipitate were washed well with dichloromethane (30 mL). The combined filtrates were concentrated in vacuo and dissolved in AcOH (7 mL). This solution was heated to 90° C. for 10 min and concentrated in vacuo. The residue was crystallized with ethyl ether (20 mL) and sonicated until a fine suspension was obtained The precipitate was filtered off and dried in vacuum to afford methyl 6-oxo-6,7,7a,8,9,10-hexahydro-5H-pyrido[3,2-b]pyrrolo[1,2-d][1,4]diazepine-3-carboxylate (0.927 g, 3.55 mmol, 72.4% yield) as a light pink solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.55-1.71 (m, 1H) 1.74-1.89 (m, 1H) 1.89-1.99 (m, 1H) 2.19 (d, J=5.81 Hz, 1H) 2.59 (dd, J=14.78, 1.64 Hz, 1H) 2.77 (dd, J=14.78, 9.98 Hz, 1H) 3.56-3.67 (m, 1H) 3.67-3.76 (m, 1H) 3.78 (s, 3H) 3.99 (td, J=9.85, 5.56 Hz, 1H) 7.64 (d, J=2.02 Hz, 1H) 8.40 (d, J=2.02 Hz, 1H) 9.73 (d, 1H) [M+H] calc'd for C13H15N3O3, 261; found, 261.

Workup

  1. filtrationThe reaction mixture was filtered through a short plug of celite
  2. washthe plug and precipitate were washed well with dichloromethane (30 mL)
  3. concentrationThe combined filtrates were concentrated in vacuo
  4. dissolutiondissolved in AcOH (7 mL)
  5. concentrationconcentrated in vacuo
  6. customThe residue was crystallized with ethyl ether (20 mL)
  7. customsonicated until a fine suspension
  8. customwas obtained The precipitate
  9. filtrationwas filtered off
  10. customdried in vacuum

Sources & evidence

ORD record
ord-9a1c6675628842a0abcd75fb7fb8496d
Source dataset
uspto-grants-2012_02
Patent number
US08124606B2

Reaction notes

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