L-Tyrosine, N-(1,1-dimethylethoxy)carbonyl- → HCID 15296358, compound

HRID 1638230Notes

Reaction equation

HRID 1638230 reaction equation
C(OC([NH:8][C@H:9]([C:14]([NH:16][CH2:17][CH2:18][CH2:19][Br:20])=[O:15])[C@H:10]([CH2:12][CH3:13])[CH3:11])=O)(C)(C)C.[C:21]([NH:28][C@H:29]([C:38]([OH:40])=O)[CH2:30][C:31]1[CH:36]=[CH:35][C:34]([OH:37])=[CH:33][CH:32]=1)([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22]>C(O)(C(F)(F)F)=O.C(Cl)Cl>[C:24]([O:23][C:21]([NH:28][C@H:29]([C:38]([NH:8][C@H:9]([C:14]([NH:16][CH2:17][CH2:18][CH2:19][Br:20])=[O:15])[C@H:10]([CH2:12][CH3:13])[CH3:11])=[O:40])[CH2:30][C:31]1[CH:32]=[CH:33][C:34]([OH:37])=[CH:35][CH:36]=1)=[O:22])([CH3:25])([CH3:26])[CH3:27]

Participants

5

Reactant 2

HCID 117439L-Tyrosine, N-(1,1-dimethylethoxy)carbonyl-HCID 15296357HCID 15296357, compound2×

Product 1

HCID 15296358HCID 15296358, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

Compound (U) (3.51 g, 10 mmol) was dissolved in a solution of 25% TFA in DCM (10 ml) and stirred at room temperature for 30 mins. The solution was evaporated to dryness in vacuo and the residue evaporated from DCM three more times to remove residual traces of TFA. This residue was coupled to Boc-tyrosine (2.8 g, 10 mmol) using the procedure described for the synthesis of compound (U). The resultant product was purified by column chromatography (silica; 50% ethyl acetate in hexane (Rf =0.19)) as a colourless powder (4.9 g, 96%), mp 96-100° C. 1H NMR (CDCl3): δ 6.7-7.1 (m, 6H, ArH, Ile-NH, NH), 5.15 (d, J=8.2 Hz, 1H, Tyr-NH), 4.30 (m, 1H, αCH), 4.2 (m, 1H, αCH), 3.35-3.50 (m, 1H, NCH), 3.40 (t, J=6.0 Hz, 2H, CH2Br), 3.25 (m, 1H, NCH), 3.01 (dd, J=6.1, 13.6 Hz, 1H, Tyr-βCH), 2.93 (dd, J=6.1, 13.6 Hz, 1H, Tyr-βCH), 2.05 (m, 2H, CH2), 1.9 (m, 1H, Ile-βCH), 1.4 (m, 10H, Ile-γCH, (CH3)3), 1.05 (m, 1H, Ile-γCH), 0.89 (d, J=6.32 Hz, 3H, Ile-γCH3), 0.83 (t, J=7.37 Hz, 3H, Ile-δCH3). ISMS 514/516 (M+H). HRMS calcd for C23H35N3O5 (M-HBr), 433.2577; found 433.2573.

Workup

  1. customThe solution was evaporated to dryness in vacuo
  2. customthe residue evaporated from DCM three more times
  3. customto remove residual traces of TFA
  4. customThe resultant product was purified by column chromatography (silica; 50% ethyl acetate in hexane (Rf =0.19)) as a colourless powder (4.9 g, 96%), mp 96-100° C

Sources & evidence

ORD record
ord-56c1c7ccdd104807acb1b2557306bddd
Source dataset
uspto-grants-2000_03
Patent number
US06043357

Reaction notes

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