Tert-butoxycarbonylalanine → N-t-butoxycarbonyl-L-alanine iodopropargyl ester

HRID 1656153Notes

Reaction equation

HRID 1656153 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:11]([OH:13])=[O:12])[CH3:10])=[O:7])([CH3:4])([CH3:3])[CH3:2].[I:14][CH:15](O)[C:16]#[CH:17].Cl.CN(C)CCCN=C=NCC>ClCCl.CN(C)C1C=CN=CC=1>[I:14][CH:15]([O:12][C:11](=[O:13])[C@H:9]([CH3:10])[NH:8][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[C:16]#[CH:17]

Participants

6

Reactant 3

HCID 85082Tert-butoxycarbonylalanineHCID 602749Iodopropargyl alcoholHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride

Product 1

HCID 57063814N-t-butoxycarbonyl-L-alanine iodopropargyl esterYield 101.7%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a magnetically stirred solution of N-t-butoxycarbonyl-L-alanine (5.00 g., 0.026 mole) and iodopropargyl alcohol (4.81 g., 0.026 mole) in anhydrous dichloromethane (100 ml.) cooled to 0° C. with an ice-bath was added 4-dimethylaminopyridine (0.32 g., 0.0026 mole) followed by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (5.57 g., 0.029 mole). The reaction mixture continued to stir at 0° C. for one hour, and was then stored in a refrigerator at 5° C. overnight. The reaction mixture was transferred to a separatory funnel and diluted to double volume (200 ml.) with dichloromethane, then washed successively with 100 ml. of water, 3×100 ml. of 10% aqueous potassium hydrogen sulfate, 100 ml. of water, 3×100 ml. of saturated aqueous sodium bicarbonate, 3×100 ml. of water and a final wash with 100 ml. of saturated aqueous sodium chloride. The organic layer was dried with magnesium sulfate, filtered and concentrated in vacuo with a rotary evaporator to a clear colorless oil which crystallized on standing. A quantitative yield (9.34 g.) of N-t-butoxycarbonyl-L-alanine iodopropargyl ester was obtained. m.p.=71°-73° C. 1H-NMR (200 MHz, DMSOd6) δ=1.25 ppm, d, 3H; 1.40, s, 9H; 4.01, m, 1H; 4.85, s, 2H; 7.33, d, 1H. IR (CHCl3) 1170, 1375, 1400, 1715, 1750, 2205 cm-1.

Workup

  1. waitwas then stored in a refrigerator at 5° C. overnight
  2. customThe reaction mixture was transferred to a separatory funnel
  3. washwashed successively with 100 ml
  4. washof water and a final wash with 100 ml
  5. dry with materialThe organic layer was dried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo with a rotary evaporator to a clear colorless oil which
  8. customcrystallized on standing

Sources & evidence

ORD record
ord-9eaefcc1a1da4c03956337dde6e448ad
Source dataset
uspto-grants-1993_10
Patent number
US05252745

Reaction notes

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