Triphenylphosphine → (1RS,2RS,4E)-2-(4-chlorophenyl)-1-methyl-5-(2-naphthyl)-4-pentenylamine

HRID 263678Notes

Reaction equation

HRID 263678 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:12]/[CH:13]=[CH:14]/[C:15]2[CH:24]=[CH:23][C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[CH:16]=2)[CH:9](O)[CH3:10])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N:44](C(OCC)=O)=NC(OCC)=O.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>O1CCCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:12]/[CH:13]=[CH:14]/[C:15]2[CH:24]=[CH:23][C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[CH:16]=2)[CH:9]([NH2:44])[CH3:10])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 199401P,P-Diphenylphosphinic azideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 19038652(2RS,3SR,5E)-3-(4-chlorophenyl)-6-(2-naphthyl)-5-hexen-2-ol

Product 1

HCID 19038665(1RS,2RS,4E)-2-(4-chlorophenyl)-1-methyl-5-(2-naphthyl)-4-pentenylamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

4.06 g of (2RS,3SR,5E)-3-(4-chlorophenyl)-6-(2-naphthyl)-5-hexen-2-ol was dissolved in 30 ml of tetrahydrofuran, and 4.77 g of triphenylphosphine, 2.89 ml of diethyl azodicarboxylate and 4.77 g of diphenylphosphoryl azide were added under cooling with ice with stirring, followed by stirring at room temperature for 30 minutes. The reaction solution was evaporated to dryness under reduced pressure. Then, the residue was purified by silica gel column chromatography (hexane/ethyl acetate=50/1→30/1). The obtained azide product was heated and refluxed together with 3.2 g of triphenylphosphine in 100 ml of 10% water-containing tetrahydrofuran. The reaction solution was evaporated to dryness under reduced pressure. Then, the residue was purified by silica gel column chromatography (methylene chloride/methanol=50/1→20/1) to obtain 2.30 g of the above-identified compound.

Workup

  1. temperatureunder cooling with ice
  2. stirringby stirring at room temperature for 30 minutes
  3. customThe reaction solution was evaporated to dryness under reduced pressure
  4. customThen, the residue was purified by silica gel column chromatography (hexane/ethyl acetate=50/1→30/1)
  5. temperatureThe obtained azide product was heated
  6. temperaturerefluxed together with 3.2 g of triphenylphosphine in 100 ml of 10% water-
  7. additioncontaining tetrahydrofuran
  8. customThe reaction solution was evaporated to dryness under reduced pressure
  9. customThen, the residue was purified by silica gel column chromatography (methylene chloride/methanol=50/1→20/1)

Sources & evidence

ORD record
ord-9fd94f574bca4effbec998a65c3ee4f4
Source dataset
uspto-grants-1997_07
Patent number
US05643958

Reaction notes

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