Triphenylphosphine → tert-butyl 4-(4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-piperidinecarboxylate

HRID 2175654Notes

Reaction equation

HRID 2175654 reaction equation
[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][NH:8][C:4]=2[N:5]=[CH:6][N:7]=1.O[CH:13]1[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([CH:13]3[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]3)[C:4]=2[N:5]=[CH:6][N:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 643502Tert-butyl 4-hydroxypiperidine-1-carboxylateHCID 5363146Diisopropyl azodicarboxylateHCID 148092816-Chloro-7-iodo-7-deazapurine

Product 1

HCID 22736256tert-butyl 4-(4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-piperidinecarboxylateYield 36%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

At −10° C. and under N2 atmosphere, to a stirred solution of 4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidine (3.0 g, 10.7 mmol), tert-butyl 4-hydroxypiperidine-1-carboxylate (5.4 g, 26.8 mmol), and PPh3 in anhydrous THF were slowly added DIAD over one hour. The resulting reaction mixture was subsequently warmed up to room temperature and stirred for additional 2 hours. Once the yellow precipitation was generated, the reaction mixture was cooled back to −5° C. and stirred overnight. While the solution was still cold, the yellow precipitation was quickly filtrated and washed with cold THF (30 mL) to afford tert-Butyl 4-(4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidin-7-yl)piperidine-1-carboxylate (62) (1.77 g, 36%) as a white solid. LC-MS (ESI): m/z (M/M+2) 463.1/465.1.

Workup

  1. customAt −10° C.
  2. customover one hour
  3. customThe resulting reaction mixture
  4. customOnce the yellow precipitation
  5. temperaturethe reaction mixture was cooled back to −5° C.
  6. stirringstirred overnight
  7. customthe yellow precipitation
  8. filtrationwas quickly filtrated
  9. washwashed with cold THF (30 mL)

Sources & evidence

ORD record
ord-1e9db630e7c04df4b743fb97e07d295f
Source dataset
uspto-grants-2015_06
Patent number
US09062058B2

Reaction notes

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