(4S)-2-Hydroxy-4-(2-methoxyphenyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide → (R)-1-amino-1-phenyl-but-3-yne 5,5-dimethyl-2-hydroxy-4-(2-methoxyphenyl)-1,3,2-dioxaphosphorinane 2-oxide

HRID 2256457Notes

Reaction equation

HRID 2256457 reaction equation
[NH2:1][CH:2]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH2:3][C:4]#[CH:5].[CH3:12][C:13]1([CH3:29])[CH2:18][O:17][P:16](=[O:20])([OH:19])[O:15][CH:14]1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[O:27][CH3:28]>C(O)C>[CH3:12][C:13]1([CH3:29])[CH2:18][O:17][P:16](=[O:19])([OH:20])[O:15][CH:14]1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[O:27][CH3:28].[NH2:1][C@@H:2]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH2:3][C:4]#[CH:5]

Participants

4

Reactant 2

HCID 5218998(4S)-2-Hydroxy-4-(2-methoxyphenyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxideHCID 12943342HCID 12943342, compound

Product 1

HCID 86751138(R)-1-amino-1-phenyl-but-3-yne 5,5-dimethyl-2-hydroxy-4-(2-methoxyphenyl)-1,3,2-dioxaphosphorinane 2-oxide

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Dissolve (RS)-1-amino-1-phenyl-but-3-yne [Zh. Org. Khim. 18(4), 980-983 (1982) A. Mostamandi, L. A. Remizova, A. L. Pavienkova, I. A. Favorskaya] (20.0 g, 138 mmol) and (-)-5,5-dimethyl-2-hydroxy-4-(2-methoxyphenyl)-1,3,2-dioxaphosphorinane 2-oxide (35.0 g, 129 mmol) in refluxing ethanol (300 mL). Cool the solution to ambient temperature and collect the precipitate by filtration. Rinse the precipitate with a small amount of isopropanol/ethanol (1/1). Two recrystallizations from ethanol gives (R)-1-amino-1-phenyl-but-3-yne 5,5-dimethyl-2-hydroxy-4-(2-methoxyphenyl)-1,3,2-dioxaphosphorinane 2-oxide salt (21 g). Combine (R)-1-amino-1-phenyl-but-3-yne 5,5-dimethyl-2-hydroxy-4-(2-methoxyphenyl)-1,3,2-dioxaphosphorinane 2-oxide salt (21 g, 50.4 mmol) with a mixture of aqueous 1M potassium hydroxide solution (100 mL) and toluene (50 mL) and stir for 0.75 hour. Separate the layers and extract the aqueous layer with toluene (50 mL), combine the organic layers, dry over (Na2SO4), and filter to obtain a solution. Pass hydrogen chloride gas through the solution until it is saturated and then remove the precipitate by filtration and rinse with toluene. Recrystallize from butanone (120 mL) to give 7.0 g the title compound. Specific rotation [α]2D0 =11.0° (c=0.500, MeOH).

Workup

  1. customcollect the precipitate
  2. filtrationby filtration
  3. washRinse the precipitate with a small amount of isopropanol/ethanol (1/1)
  4. customTwo recrystallizations from ethanol

Sources & evidence

ORD record
ord-99f9e8f8dc764f5c8c1f0d88f2ed6573
Source dataset
uspto-grants-1997_08
Patent number
US05654477

Reaction notes

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