Triphenylphosphine → Triphenylphosphine Oxide

HRID 1852329Notes

Reaction equation

HRID 1852329 reaction equation
C([O:5]C(N1CCC[C@H]1CO)=O)(C)(C)C.[C:15]1([P:21]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.N1C=CC(=O)NC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C(Cl)Cl>[C:28]1([P:21](=[O:5])([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 206954-HydroxypyrimidineHCID 643448(S)-(-)-N-Boc-prolinol2×HCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 13097Triphenylphosphine Oxide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of N-tert-butoxycarbonyl-L-prolinol (0.81 g, 4 mmol) 18 in dry DCM (10 mL) was added triphenylphosphine (5.24 g, 20 mmol) followed by 4(3H)-pyrimidone (0.77 g, 8 mmol). The solution was cooled in an ice bath and DIAD (3.24 g, 16 mmol) added dropwise over 10 min. After 48 h GC-MS indicated complete conversion of 18 and the reaction mixture was poured onto water (30 mL), the organic fraction collected and the aqueous phase washed with further DCM (2×20 mL). The combined organic fractions were washed with 1M NaOH (2×15 mL) then brine (1×15 mL) and dried over Na2SO4. Removal of bulk solvent yielded an orange gum, addition of hexanes/diethyl ether (1:1) resulted in formation of a precipitate of triphenylphosphine oxide, which was removed by filtration. Chromatography (ethyl acetate) afforded the desired product as a colorless oil (0.77 g, 69%). HRMS (ESI)=280.1655 (M+H)+. Calcd. for C14H22N3O3 280.1656. 1H NMR (600 MHz, CDCl3) δ 8.71 (s, 1H), 8.39 (d, J=6 Hz, 1H), 6.69 (d, J=6 Hz, 1H), 4.45-3.91 (m, 3H), 3.40-3.33 (m, 2H), 2.00-1.82 (m, 4H), 1.42 (s, 9H). TLC (UV254) Rf=0.49 (ethyl acetate).

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. customthe organic fraction collected
  3. washthe aqueous phase washed with further DCM (2×20 mL)
  4. washThe combined organic fractions were washed with 1M NaOH (2×15 mL)
  5. dry with materialbrine (1×15 mL) and dried over Na2SO4
  6. customRemoval of bulk solvent
  7. customyielded

Sources & evidence

ORD record
ord-dcaf581317ec423cb7967a3ab2490755
Source dataset
uspto-grants-2015_02
Patent number
US08961930B2

Reaction notes

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