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

HRID 53455노트

반응식

HRID 53455 반응식
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]

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 6436379Rhodium, di-mu-chlorobis((1,2,5,6-eta)-1,5-cyclooctadiene)di-촉매HCID 887Methanol용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-3c3e1f380b774e1db8bd5dc9e1390471
출처 데이터셋
uspto-grants-1997_04
특허 번호
US05618970

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