Triphenylphosphine → HCID 131720782, compound

HRID 481711Notes

Reaction equation

HRID 481711 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.[Si:34]([O:51][CH2:52][CH:53]([OH:58])[C:54]([O:56][CH3:57])=[O:55])([C:47]([CH3:50])([CH3:49])[CH3:48])([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.[C:59](O)(=[S:61])[CH3:60]>C1COCC1>[Si:34]([O:51][CH2:52][CH:53]([O:58][C:59](=[S:61])[CH3:60])[C:54]([O:56][CH3:57])=[O:55])([C:47]([CH3:50])([CH3:49])[CH3:48])([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 21255857HCID 21255857, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 131720782HCID 131720782, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of triphenylphosphine (101 g, 385 mmol, 2 eq) in THF (1.5 L) was added diisopropylazodicarboxylate (76 mL, 386 mmol, 2 eq) at 0° C. The mixture was stirred at 0° C. for 1 hr and was followed by the addition of a solution of methyl 3-t-butyldiphenylsilyloxy-2-hydroxypropionate (example 39) (68.89 g, 192 mmol) and thioacetic acid (27.6 mL, 386 mmol, 2 eq.) in THF, to the same temperature. The mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr. The solution was concentrated to dryness and the solid was washed with hexane (5×300 mL). The organic solution was filtered and evaporated under reduced pressure. The crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (95:5) to give the pure compound (49.3 g) in 62% yield. 1H NMR (300 MHz, CDCl3) δ: 1.03 (s, 9H, t-butyl), 2.35 (s, 3H, SCOCH3), 3.75 (s, 3H, CO2CH3), 3.93 (dd, 1H, J=6.6 Hz, 9.9 Hz, H-3a), 4.01 (dd, 1H, J=4.9 Hz, 9.9 Hz, H-3b), 4.45 (dd, 1H, J=6.8 Hz, 4.9 Hz, H-2), 7.42 and 7.64 (m, 10H, Ar-H).

Workup

  1. stirringThe mixture was stirred at 0° C. for 1 hr and at room temperature for 18 hr
  2. concentrationThe solution was concentrated to dryness
  3. washthe solid was washed with hexane (5×300 mL)
  4. filtrationThe organic solution was filtered
  5. customevaporated under reduced pressure
  6. customThe crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (95:5)

Sources & evidence

ORD record
ord-55e29f89a6d14eff8e26da81b44201f2
Source dataset
uspto-grants-1998_08
Patent number
US05789394

Reaction notes

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