Triphenylphosphine → HCID 58365196, compound

HRID 60336Notes

Reaction equation

HRID 60336 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[C:15]2[CH:16]=[N:17][CH:18]=[C:19]([OH:20])[C:14]=2[C:13]2[CH:21]=[C:22]([Br:25])[CH:23]=[N:24][C:12]1=2)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:26]([O:30][C:31]([N:33]1[CH2:38][CH2:37][CH:36](O)[CH2:35][CH2:34]1)=[O:32])([CH3:29])([CH3:28])[CH3:27].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH2:1]([O:8][C:9]([N:11]1[C:15]2[CH:16]=[N:17][CH:18]=[C:19]([O:20][CH:36]3[CH2:37][CH2:38][N:33]([C:31]([O:30][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:32])[CH2:34][CH2:35]3)[C:14]=2[C:13]2[CH:21]=[C:22]([Br:25])[CH:23]=[N:24][C:12]1=2)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 643502Tert-butyl 4-hydroxypiperidine-1-carboxylateHCID 58365044HCID 58365044, compound

Product 1

HCID 58365196HCID 58365196, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 3-bromo-5-hydroxy-dipyrido[2,3-b;4′,3′-d]pyrrole-9-carboxylic acid benzyl ester (234 mg, 0.59 mmol), 4-hydroxypiperidine-1-carboxylic acid tert-butyl ester (295 mg, 1.47 mmol) and triphenylphosphine (390 mg, 1.47 mmol) in anhydrous THF (7 mL) was treated dropwise with diethyl azodicarboxylate (295 mg, 1.47 mmol). On complete addition the mixture was heated at 50° C. for 1 hour. The mixture was concentrated in-vacuo and the resultant residue was purified by flash chromatography (silica, 12 g cartridge, ISCO, 0-7% methanol in dichloromethane). The appropriate fractions were collected and evaporated to afford the title compound as an orange oil (0.34 g, 100%). LCMS (Method B): RT=4.76 min, M+H+=581/583. 1H NMR (400 MHz, CDCl3): 9.27 (s, 1H), 8.80 (d, J=2.3 Hz, 1H), 8.61 (d, J=2.3 Hz, 1H), 8.32 (s, 1H), 7.60 (d, J=7.3 Hz, 2H), 7.43-7.36 (m, 3H), 5.64 (s, 2H), 4.89 (m, 1H), 3.40-3.39 (m, 2H), 3.02 (ddd, J=13.5, 9.8, 3.4 Hz, 2H), 2.21-1.80 (m, 4H), 1.46 (s, 9H).

Workup

  1. additionOn complete addition the mixture
  2. concentrationThe mixture was concentrated in-vacuo
  3. customthe resultant residue was purified by flash chromatography (silica, 12 g cartridge, ISCO, 0-7% methanol in dichloromethane)
  4. customThe appropriate fractions were collected
  5. customevaporated

Sources & evidence

ORD record
ord-adadba91a66b4da0b274fc0ca93fec94
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Reaction notes

Loading…