Triphenylphosphine → tert-butyl 4-(4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)piperidine-1-carboxylate

HRID 916784Notes

Reaction equation

HRID 916784 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[Cl:13][C:14]1[C:15]2[CH:22]=[CH:21][NH:20][C:16]=2[N:17]=[CH:18][N:19]=1.[C:23]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33](O)[CH2:32][CH2:31]1)=[O:29])([CH3:26])([CH3:25])[CH3:24].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[C:23]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33]([N:20]2[C:16]3[N:17]=[CH:18][N:19]=[C:14]([Cl:13])[C:15]=3[CH:22]=[CH:21]2)[CH2:32][CH2:31]1)=[O:29])([CH3:26])([CH3:24])[CH3:25]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 643502Tert-butyl 4-hydroxypiperidine-1-carboxylateHCID 53566827H-Pyrrolo(2,3-d)pyrimidine, 4-chloro-

Product 1

HCID 58270310tert-butyl 4-(4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)piperidine-1-carboxylateYield 93%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Diethyl azodicarboxylate (14.4 g, 82.7 mmol) was added dropwise over a period of 1 h (exothermic) to a solution of 4-chloro-7H-pyrrolo[2,3-d]pyrimidine (6.4 g, 41.4 mmol), 4-hydroxy-piperidine-1-carboxylic acid tert-butyl ester (25.0 g, 124 mmol), and triphenyl phosphine 21.7 g, 82.7 mmol) in THF (500 mL). The reaction mixture was stirred at room temperature 3 h and concentrated in vacuo. The crude reaction mixture was washed with EtOAc, filtered, and concentrated in vacuo. Purification by flash column chromatography (silica, 5:95→15:85 EtOAc:hexanes) provided the title compound as a white solid (6.5 g, 93%). MS: 338 (MH+); HPLC Rf: 6.21 min. (HPLC method 4); HPLC purity: 91%.

Workup

  1. concentrationconcentrated in vacuo
  2. customThe crude reaction mixture
  3. washwas washed with EtOAc
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification by flash column chromatography (silica, 5:95→15:85 EtOAc:hexanes)

Sources & evidence

ORD record
ord-01ec13bcdc264b1ebaa0d68dfdbd4265
Source dataset
uspto-grants-2007_09
Patent number
US07271262B2

Reaction notes

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