Pyridine → (S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-(((trifluoromethyl)sulfonyl)oxy)phenyl)propanoate

HRID 1530934Notes

Reaction equation

HRID 1530934 reaction equation
[F:1][C:2]([F:15])([F:14])[S:3]([O:6]S(C(F)(F)F)(=O)=O)(=[O:5])=[O:4].[CH3:16][O:17][C:18](=[O:36])[C@H:19]([CH2:28][C:29]1[CH:34]=[CH:33][C:32](O)=[CH:31][CH:30]=1)[NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22].N1C=CC=CC=1>C(Cl)Cl.O>[CH3:16][O:17][C:18](=[O:36])[C@H:19]([CH2:28][C:29]1[CH:30]=[CH:31][C:32]([O:6][S:3]([C:2]([F:15])([F:14])[F:1])(=[O:5])=[O:4])=[CH:33][CH:34]=1)[NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:25])[CH3:26])=[O:22]

Participants

6

Reactant 3

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 7019130Boc-Tyr-OMe

Product 1

HCID 10455198(S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-(((trifluoromethyl)sulfonyl)oxy)phenyl)propanoateYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

Trifluoromethanesulphonic anhydride (4 ml, 23 mmol) was added to a mixture of N-Boc tyrosine methyl ester (5.9 g, 20 mmol) and pyridine (8 ml, 100 mmol) in DCM (30 ml) at 0°. After 30 min the reaction mixture was diluted with water (60 ml) and DCM (100 ml) and washed with aqueous NaOH (0.5M, 50 ml), water (60 ml), citric acid (10% solution, 2×75 ml) and water (60 ml), dried (Na2SO4) and evaporated in vacuo. Purification by column chromatography (SiO2; EtOAc/hexane, 2:1) gave the title compound (7.76 g, 91%) as a colourless oil which solidified on standing. δH (CDCl3) 7.25-7.18 (4 H, m, ArH), 5.01 (1 H, brd, CONH), 4.60 (1 H, brq, CHα), 3.71 (3 H, s, CO2Me), 3.17 (1 H, dd, J 13.8, 5.8 Hz, CHAHBAr), 3.03 (1 H, dd, J 13.6, 6.3 Hz, CHAHBAr) and 1.41 (9 H, s, tBu); m/z (ESI, 15 V) 428 (MH+).

Workup

  1. washwashed with aqueous NaOH (0.5M, 50 ml), water (60 ml), citric acid (10% solution, 2×75 ml) and water (60 ml)
  2. dry with materialdried (Na2SO4)
  3. customevaporated in vacuo
  4. customPurification by column chromatography (SiO2; EtOAc/hexane, 2:1)

Sources & evidence

ORD record
ord-b6b9f79cbd0a4e56891e680ba42b5a14
Source dataset
uspto-grants-2001_03
Patent number
US06197794B1

Reaction notes

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