Triphenylphosphine → HCID 57812376, compound

HRID 912016Notes

Reaction equation

HRID 912016 reaction equation
C(OC([N:8]1[CH2:13][CH2:12][CH:11]([N:14]2[CH:18]=[C:17]([C:19]3[C:23]4[CH:24]=[N:25][C:26]([N+:29]([O-])=O)=[C:27](O)[C:22]=4[O:21][CH:20]=3)[CH:16]=[N:15]2)[CH2:10][CH2:9]1)=O)(C)(C)C.[Cl:32][C:33]1[CH:38]=[CH:37][CH:36]=[C:35]([Cl:39])[C:34]=1[CH:40]([OH:43])[CH2:41][CH3:42].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>Cl.[Fe].C1COCC1>[Cl:32][C:33]1[CH:38]=[CH:37][CH:36]=[C:35]([Cl:39])[C:34]=1[CH:40]([O:43][C:27]1[C:22]2[O:21][CH:20]=[C:19]([C:17]3[CH:16]=[N:15][N:14]([CH:11]4[CH2:12][CH2:13][NH:8][CH2:9][CH2:10]4)[CH:18]=3)[C:23]=2[CH:24]=[N:25][C:26]=1[NH2:29])[CH2:41][CH3:42]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 12105278HCID 12105278, compoundHCID 578125344-[4-(7-Hydroxy-6-nitrofuro[3,2-c]pyridin-3-yl)pyrazol-1-yl]piperidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 57812376HCID 57812376, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 23925IronCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

General procedure AA: To a mixture of 4-[4-(7-hydroxy-6-nitrofuro[3,2-c]pyridine-3-yl)-pyrazol-1-yl]-piperidine-1-carboxylic acid tert-butyl ester (20.0 mg, 0.047 mmol), 1-(2,6-dichlorophenyl)propan-1-ol (28.6 mg, 0.14 mmol), triphenylphosphine (24.4 mg, 0.093 mmol) and THF (2 mL) at rt was added diisopropyl azodicarboxylate (37.7 mg, 0.186 mmol) dropwise, and the solution was flushed with nitrogen and heated to 50° C. for 4 h. The solvents were removed in vacuo, and the material was redissolved in EtOH (3 mL). Iron powder (30 mg, 0.5 mmol) and 5 drops of conc. HCl were added, and the solution was refluxed for 30 min. The solution was directly passed through a SCX cartridge, washed with MeOH and ejected with 2M NH3 in MeOH. The crude product was concentrated in vacuo, redissolved MeOH (1 mL) and purified via HPLC. The fractions containing the pure product were concentrated in vacuo to afford the title compound as a white solid. 1H NMR (400 MHz, CD3OD): δ=1.06 (t, J=7.5 Hz, 3H), 1.93-2.05 (m, 2H), 2.09-2.17 (m, 2H), 2.33 (dt, J=13.7, 7.5 Hz, 1H), 2.48 (dd, J=14.3, 6.9 Hz, 1H), 2.78 (td, J=12.7, 2.7 Hz, 2H), 3.16-3.24 (m, 2H), 4.35 (tt, J=11.7, 4.1 Hz, 1H), 6.43 (t, J=7.5 Hz, 1H), 7.20-7.26 (m, 1H), 7.36 (d, J=8.1 Hz, 2H), 7.80 (s, 1H), 7.83 (s, 1H), 8.09 (s, 1H), 8.13 (s, 1H). MS (ES+): m/z 498.06/500.05 (100/72) [MH+]. HPLC: tR=2.65 min (ZQ3, polar—5 min).

Workup

  1. customthe solution was flushed with nitrogen
  2. customThe solvents were removed in vacuo
  3. dissolutionthe material was redissolved in EtOH (3 mL)
  4. temperaturethe solution was refluxed for 30 min
  5. washwashed with MeOH
  6. concentrationThe crude product was concentrated in vacuo
  7. dissolutionredissolved MeOH (1 mL)
  8. custompurified via HPLC
  9. additionThe fractions containing the pure product
  10. concentrationwere concentrated in vacuo

Sources & evidence

ORD record
ord-8695840dd75b4b0fa82e1679ae996a0b
Source dataset
uspto-grants-2011_09
Patent number
US08022206B2

Reaction notes

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