Binap, (A+-)- → (S)-1-[2-(tert-Butoxycarbonyl)-3-(2-methoxyethoxy)propyl]-1-cyclopentanecarboxylic acid cyclohexylamine salt

HRID 53455ノート

反応式

HRID 53455 の反応式
C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[CH:47]1([NH2:53])[CH2:52][CH2:51][CH2:50][CH2:49][CH2:48]1.[C:54]([O:58][C:59](/[C:61](/[CH2:71][O:72][CH2:73][CH2:74][O:75][CH3:76])=[CH:62]/[C:63]1([C:68]([OH:70])=[O:69])[CH2:67][CH2:66][CH2:65][CH2:64]1)=[O:60])([CH3:57])([CH3:56])[CH3:55]>CO.C1CC=CCCC=C1.C1CC=CCCC=C1.[Cl-].[Cl-].[Rh].[Rh]>[CH:47]1([NH2:53])[CH2:52][CH2:51][CH2:50][CH2:49][CH2:48]1.[C:54]([O:58][C:59]([C@H:61]([CH2:71][O:72][CH2:73][CH2:74][O:75][CH3:76])[CH2:62][C:63]1([C:68]([OH:70])=[O:69])[CH2:67][CH2:66][CH2:65][CH2:64]1)=[O:60])([CH3:56])([CH3:55])[CH3:57]

参加物

5

反応物 2

HCID 634876Binap, (A+-)-HCID 67726576(E)-1-[2-(tert-butoxycarbonyl)-3-(2-methoxyethoxy)prop-1-enyl]-1-cyclopentanecarboxylic acid cyclohexylamine salt

生成物 1

HCID 67726561(S)-1-[2-(tert-Butoxycarbonyl)-3-(2-methoxyethoxy)propyl]-1-cyclopentanecarboxylic acid cyclohexylamine salt収率 74%

試薬・触媒・溶媒 2

HCID 6436379Rhodium, di-mu-chlorobis((1,2,5,6-eta)-1,5-cyclooctadiene)di-触媒HCID 887Methanol溶媒

実験手順

Chloro(1,5-cyclooctadiene)rhodium(I)dimer (15.2 mg, 0.03 mmole) and (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (42.2 mg, 0.06 mmole) were charged to a 50 mL three necked flask equiped with gas inlet and outlet lines and the third neck sealed with a rubber septum. The system was flushed with nitrogen, methanol (10 mL) was added and the mixture purged with nitrogen for 30 minutes. The reaction was hydrogenated at atmospheric hydrogen pressure and room temperature for 1 hour. At this point a solution of (E)-1-[2-(tert-butoxycarbonyl)-3-(2-methoxyethoxy)prop-1-enyl]-1-cyclopentanecarboxylic acid cyclohexylamine salt (0.5 g, 1.17 mmol) in methanol (10 mL) was added and the mixture hydrogenated at atmospheric pressure and room temperature for 5 days. The reaction mixture was purged with nitrogen and concentrated under reduced pressure to give a brown solid (Ratio S:R 89:11). The crude product was recrystallised from ethyl acetate (3.5 ml) and hexane (3.5 ml) to give the title compound (0.37 g, 74%). (Ratio S:R 92:8), Rf =0.29 (ethyl acetate/hexane, 1:1+1% acetic acid).

後処理

  1. customequiped with gas inlet and outlet lines
  2. customthe third neck sealed with a rubber septum
  3. customThe system was flushed with nitrogen, methanol (10 mL)
  4. additionwas added
  5. customthe mixture purged with nitrogen for 30 minutes
  6. waitthe mixture hydrogenated at atmospheric pressure and room temperature for 5 days
  7. customThe reaction mixture was purged with nitrogen
  8. concentrationconcentrated under reduced pressure
  9. customto give a brown solid (Ratio S:R 89:11)
  10. customThe crude product was recrystallised from ethyl acetate (3.5 ml) and hexane (3.5 ml)

出典と根拠

ORDレコード
ord-3c3e1f380b774e1db8bd5dc9e1390471
出典データセット
uspto-grants-1997_04
特許番号
US05618970

反応ノート

読み込み中…