Nitrogen → HCID 10087791, compound

HRID 1609384Notes

Reaction equation

HRID 1609384 reaction equation
N#N.[C:3]1([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:8]=[CH:7][C:6]([CH:9]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C:10](OC)=[O:11])=[CH:5][CH:4]=1.C(=O)=O.CC(C)=O.CC(C[AlH]CC(C)C)C>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[C:3]1([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH:8]=[CH:7][C:6]([C@@H:9]([O:14][Si:15]([C:18]([CH3:20])([CH3:21])[CH3:19])([CH3:17])[CH3:16])[CH:10]=[O:11])=[CH:5][CH:4]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 14487Diisobutylaluminum hydrideHCID 18522661Acetone cardiceHCID 85108976HCID 85108976, compound

Product 1

HCID 10087791HCID 10087791, compoundYield 95.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 6212ChloroformSolvent

Procedure

A 100 mL 2-necked round bottom flask was equipped with a septum, N2 inlet and 2.6 g (7.4 mmol) of the (R)-(-)-methyl acetate of Example O dissolved in 45 mL of dry toluene. The solution was cooled to -78° C. (CO2 /acetone), and 9 mL (9 mmol) of a 1.0M solution of DIBAL-H in toluene was added slowly (5 min.) with stirring. The reaction mixture was stirred for 1 h at -78° C. and poured into a mixture of 100 g of ice and 100 mL of CHCl3. The reaction flask was rinsed with 100 mL of CHCl3 and the mixture was stirred vigorously for 30 min. After separation of the CHCl3 layer, the aqueous phase was washed with 100 mL of CHCl3 (emulsion!) and the combined CHCl3 extracts were washed once with brine 80 mL, dried (Na2SO4) and concentrated leaving 2.3 g (95%) of the title aldehyde as a colorless oil which was not further purified: 1H-NMR (CDCl3)δ9.54 (d, J=2.1 Hz, 1H), 7.63-7.35 (m, 9H), 5.05 (d, J=2.1 Hz, 1H), 0.97 (s, 9H), 0.14 (s, 3H), 0.07 (s, 3H).

Workup

  1. additionwas added slowly (5 min.)
  2. stirringThe reaction mixture was stirred for 1 h at -78° C.
  3. washThe reaction flask was rinsed with 100 mL of CHCl3
  4. stirringthe mixture was stirred vigorously for 30 min
  5. customAfter separation of the CHCl3 layer
  6. washthe aqueous phase was washed with 100 mL of CHCl3 (emulsion!)
  7. washthe combined CHCl3 extracts were washed once with brine 80 mL
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-6a94fbeb392a46b1904c9c8c8f79d23a
Source dataset
uspto-grants-1995_03
Patent number
US05399721

Reaction notes

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