Triphenyl phosphite → (S)-3-bromo-6a,7,8,9-tetrahydropyrido[3,2-e]pyrrolo[1,2-a]pyrazin-6(5H)-one

HRID 716346

反応式

HRID 716346 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([N+:18]([O-])=O)[C:5]([N:8]2[CH2:12][CH2:11][CH2:10][C@H:9]2[C:13](OCC)=[O:14])=[N:6][CH:7]=1.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1>ClCCl.[NH4+].[O-][V](=O)=O.[Pt]>[Br:1][C:2]1[CH:7]=[N:6][C:5]2[N:8]3[CH2:12][CH2:11][CH2:10][C@H:9]3[C:13](=[O:14])[NH:18][C:4]=2[CH:3]=1

参加物

6

反応物 2

HCID 7540Triphenyl phosphiteHCID 58324356(S)-ethyl 1-(5-bromo-3-nitropyridin-2-yl)pyrrolidine-2-carboxylate

生成物 1

HCID 58324379(S)-3-bromo-6a,7,8,9-tetrahydropyrido[3,2-e]pyrrolo[1,2-a]pyrazin-6(5H)-one収率 42.8%

試薬・触媒・溶媒 3

HCID 23939Platinum触媒HCID 516859Ammonium metavanadate触媒HCID 6344Dichloromethane溶媒

実験手順

(S)-ethyl 1-(5-bromo-3-nitropyridin-2-yl)pyrrolidine-2-carboxylate (8.6 g, 24.99 mmol) was dissolved in dichloromethane (Volume: 125 ml) and to this solution was added triphenyl phosphite (0.078 g, 0.250 mmol), ammonium metavanadate (0.175 g, 1.499 mmol) and Pt/C (5% wt.) (0.975 g, 0.250 mmol). The reaction mixture was hydrogenated at 80 psi at 25° C. for 4 h. The reaction mixture was filtered through celite using DCM and MeOH to complete the transfer and wash the celite plug. The combined filtrates and washes were concentrated in vacuo and crystallized with ethyl ether (75 mL). The precipitate was filtered and dried in vacuum to afford (S)-3-bromo-6a,7,8,9-tetrahydropyrido[3,2-e]pyrrolo[1,2-a]pyrazin-6(5H)-one (2.87 g, 10.70 mmol, 42.8% yield) as a pale beige solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.82-2.03 (m, 3H) 2.11-2.26 (m, 1H) 3.27-3.47 (m, 1H) 3.49-3.63 (m, 1H) 4.01-4.11 (m, 1H) 7.06 (d, J=2.27 Hz, 1H) 7.77 (d, J=2.02 Hz, 1H) 10.57 (s, 1H). [M+H] calc'd for C10H10BrN3O, 268. found, 268.

後処理

  1. filtrationThe reaction mixture was filtered through celite
  2. washwash the celite plug
  3. concentrationThe combined filtrates and washes were concentrated in vacuo
  4. customcrystallized with ethyl ether (75 mL)
  5. filtrationThe precipitate was filtered
  6. customdried in vacuum

出典と根拠

ORDレコード
ord-c95cfe3210444a5b9d36536428391755
出典データセット
uspto-grants-2015_11
特許番号
US09187497B2

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