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

HRID 53455Notes

Reaction equation

HRID 53455 reaction equation
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]

Participants

5

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 2

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

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-3c3e1f380b774e1db8bd5dc9e1390471
Source dataset
uspto-grants-1997_04
Patent number
US05618970

Reaction notes

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