Triphenylphosphine → HCID 131730338, compound

HRID 1948383Notes

Reaction equation

HRID 1948383 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[C:34]([O:38][C:39]([N:41]1[CH2:46][CH2:45][CH:44]([N:47]=[C:48]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[CH:43](O)[CH2:42]1)=[O:40])([CH3:37])([CH3:36])[CH3:35].P([N:78]=[N+:79]=[N-:80])(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O>C1COCC1>[C:34]([O:38][C:39]([N:41]1[CH2:46][CH2:45][C@H:44]([N:47]=[C:48]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[C:49]2[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=2)[C@H:43]([N:78]=[N+:79]=[N-:80])[CH2:42]1)=[O:40])([CH3:37])([CH3:36])[CH3:35]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 123414Diphenylphosphoryl azideHCID 5363146Diisopropyl azodicarboxylateHCID 87481887HCID 87481887, compound2×

Product 1

HCID 131730338HCID 131730338, compoundYield 71.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

In a flame-dried flask triphenylphosphine (3.86 g; 14.7 mmol; 2 eq.) was dissolved in anhydrous THF (15 ml) and cooled to 0 C. DIAD (2.97 g; 14.7 mmol; 2 eq.) was slowly added dropwise. Upon addition a white precipitate formed. A THF solution containing tert-butyl-4-[(diphenylmethylene)amino]-3-hydroxypiperidine-1-carboxylate (Intermediate 268, 2.8 g; 7.36 mmol) was added (amount of THF added was such that the final concentration of alcohol was ca. 0.5-1M). The resultant reaction slurry was stirred at 0 C for 30 minutes. (PhO)2PON3 (4.05 g; 14.7 mmol; 2 eq.) was then added and the reaction was allowed to warm to RT and stirred for 12 hrs. Monitored by LC/MS. The reaction was concentrated and purified by flash column chromatography (0-30% EtOAc/hexanes with 0.1% triethylamine). Isolation gave 2.13 g of the title compound in 71% yield. LC/MS (ES+)[(M+H)+]: 406 for C23H27N5O2.

Workup

  1. temperaturecooled to 0 C
  2. additionUpon addition a white precipitate
  3. customformed
  4. additionadded
  5. customThe resultant reaction slurry
  6. stirringstirred for 12 hrs
  7. concentrationThe reaction was concentrated
  8. custompurified by flash column chromatography (0-30% EtOAc/hexanes with 0.1% triethylamine)

Sources & evidence

ORD record
ord-d17308243e794bc2807c7b1cceccdf2e
Source dataset
uspto-grants-2013_03
Patent number
US08399489B2

Reaction notes

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