Hydrochloric Acid → HCID 86626944, compound

HRID 1695321Notes

Reaction equation

HRID 1695321 reaction equation
C[O:2][C:3](=O)[C@@H:4]1[CH2:8][C:7](=[CH2:9])[CH2:6][N:5]1[C:10](=[O:29])[C:11]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([O:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][Br:25])=[CH:13][C:12]=1[N+:26]([O-:28])=[O:27].CC(C[AlH]CC(C)C)C.Cl>C1(C)C=CC=CC=1.C(Cl)Cl.C1(C)C=CC=CC=1.CO>[Br:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][O:19][C:14]1[C:15]([O:17][CH3:18])=[CH:16][C:11]([C:10]([N:5]2[CH2:6][C:7](=[CH2:9])[CH2:8][C@H:4]2[CH:3]=[O:2])=[O:29])=[C:12]([N+:26]([O-:28])=[O:27])[CH:13]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 14487Diisobutylaluminum hydrideHCID 67145028HCID 67145028, compound

Product 1

HCID 86626944HCID 86626944, compoundYield 80.5%

Reagents, catalysts & solvents 3

HCID 887MethanolCatalystHCID 1140TolueneSolventHCID 21877217Toluene methylene chlorideSolvent

Conditions

Temperature
0 °C

Procedure

To a vigorously stirred solution of 1-[4-(5-bromopentyloxy)-5-methoxy-2-nitro-benzoyl]-4-methylene-L-proline methyl ester 18 (61 mg, 0.12 mmol) in anhydrous toluene —CH2Cl2 (3:1, 2.5 mL) was added dropwise solution of DIBAL-H (188 μL of a 1M solution in toluene) at −78° C. under argon atmosphere. After the mixture was stirred for an additional 45 min, excess reagent was decomposed by addition of three drops of methanol followed by 5% HCl (2 mL). The resulting mixture was allowed to warm to 0° C. Layers were separated and the aqueous layer was further extracted with CH2Cl2 (3×2 mL). Combined organic layers were washed with brine, and dried (MgSO4) and concentrated. Purification of the residue by flash chromatography (silica gel, 1:1 hexanes/EtOAc) yielded (S)-1-[4-(5-bromopentyloxy)-5-methoxy-2-nitro-benzoyl]-4-methylene-2-pyrrolidinecarboxaldehyde 19 as light yellow oil (44 mg, 80%).

Workup

  1. customLayers were separated
  2. extractionthe aqueous layer was further extracted with CH2Cl2 (3×2 mL)
  3. washCombined organic layers were washed with brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customPurification of the residue by flash chromatography (silica gel, 1:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-7b185eeec6e84b14a84ddcc4e38aa67f
Source dataset
uspto-grants-2012_04
Patent number
US08163736B2

Reaction notes

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