Triethylamine → Tert-butyl (S)-Nalpha-[(S)-1-carbethoxy-3-phenylpropyl]-Nepsilon-benzyloxycarbonyllysinate

HRID 1032685Notes

Reaction equation

HRID 1032685 reaction equation
Cl.[CH2:2]([O:9][C:10]([NH:12][CH2:13][CH2:14][CH2:15][CH2:16][C@@H:17]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[NH2:18])=[O:11])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C(N(CC)CC)C.O=[C:34]([CH2:40][CH2:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)[C:35]([O:37][CH2:38][CH3:39])=[O:36].C([BH3-])#N.[Na+]>C(O)C>[C:35]([C@@H:34]([NH:18][C@H:17]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:16][CH2:15][CH2:14][CH2:13][NH:12][C:10]([O:9][CH2:2][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1)=[O:11])[CH2:40][CH2:41][C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1)([O:37][CH2:38][CH3:39])=[O:36]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 562087Ethyl alpha-oxobenzenebutanoateHCID 5003444Sodium cyanoborohydrideHCID 13536460(S)-tert-butyl 2-amino-6-(((benzyloxy)carbonyl)amino)hexanoate hydrochloride

Product 1

HCID 14406836Tert-butyl (S)-Nalpha-[(S)-1-carbethoxy-3-phenylpropyl]-Nepsilon-benzyloxycarbonyllysinate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
20 °C

Procedure

10 g (0.0268 mol) of tert-butyl Nε -benzyloxycarbonyllysinate hydrochloride are dissolved in 150 cm3 of anhydrous ethanol; 2.71 g (0.0268 mol) of triethylamine, 20.6 g (0.1 mol) of ethyl 2-oxo-4-phenylbutyrate and 20 g of 4Å molecular sieve are added. The mixture is stirred for one hour at 20° C. A solution of 1.68 g (0.0268 mol) of sodium cyanoborohydride in 20 cm3 of ethanol is then added in the course of 4 hours, after which stirring is continued for 18 hours at 20° C. The mixture is filtered and taken to dryness, the residue is redissolved in 200 cm3 of ethyl acetate and the solution is then washed twice with 100 cm3 of a 10% strength aqueous citric acid solution and then with water until the washing liquors are neutral. The mixture is dried over magnesium sulfate and evaporated. 28.7 g of an oil are collected, and this is purified by chromatography on silica gel (eluent: methylene chloride/acetone 95:5). After the removal of impurities and then the (S, R) isomer, 4.1 g of tert-butyl (S)-Nα -[(S)-1-carbethoxy-3-phenylpropyl]-Nε -benzyloxycarbonyllysinate are collected, and used without further treatment in the following stage.

Workup

  1. stirringafter which stirring
  2. waitis continued for 18 hours at 20° C
  3. filtrationThe mixture is filtered
  4. dissolutionthe residue is redissolved in 200 cm3 of ethyl acetate
  5. washthe solution is then washed twice with 100 cm3 of a 10% strength aqueous citric acid solution
  6. dry with materialThe mixture is dried over magnesium sulfate
  7. customevaporated
  8. custom28.7 g of an oil are collected
  9. customthis is purified by chromatography on silica gel (eluent: methylene chloride/acetone 95:5)
  10. customAfter the removal of impurities
  11. customthe (S, R) isomer, 4.1 g of tert-butyl (S)-Nα -[(S)-1-carbethoxy-3-phenylpropyl]-Nε -benzyloxycarbonyllysinate are collected

Sources & evidence

ORD record
ord-394ba057c8ae40f99e84a9fdc37d94c6
Source dataset
uspto-grants-1990_09
Patent number
US04959372

Reaction notes

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