(S)-methyl 4-(tert-butoxycarbonylamino)-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate → (S)-methyl 4-amino-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate

HRID 333132Notes

Reaction equation

HRID 333132 reaction equation
C(OC([NH:8][C@H:9]([C:16]([NH:18][C@@H:19]([CH2:31][CH2:32][C:33]([O:35][CH3:36])=[O:34])[C:20]([NH:22][CH2:23][C:24]1[CH:29]=[CH:28][C:27]([I:30])=[CH:26][CH:25]=1)=[O:21])=[O:17])[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])=O)(C)(C)C>C(Cl)Cl.C(O)(C(F)(F)F)=O>[NH2:8][C@H:9]([C:16]([NH:18][C@@H:19]([CH2:31][CH2:32][C:33]([O:35][CH3:36])=[O:34])[C:20]([NH:22][CH2:23][C:24]1[CH:25]=[CH:26][C:27]([I:30])=[CH:28][CH:29]=1)=[O:21])=[O:17])[CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13]

Participants

4

Reactant 1

HCID 68630252(S)-methyl 4-(tert-butoxycarbonylamino)-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate

Product 1

HCID 68632742(S)-methyl 4-amino-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

A solution of (S)-methyl 4-(tert-butoxycarbonylamino)-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate (0.448 g, 0.723 mmol) in DCM (10 mL) and TFA (4.0 mL) was stirred at room temperature overnight. After the solvent was evaporated, the reaction mixture was diluted with DCM, washed with sat. K2CO3 and concentrated in vacuo to afford (S)-methyl 4-amino-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate. A solution of the above product ((S)-methyl 4-amino-5-((S)-1-(4-iodobenzylamino)-5-methoxy-1,5-dioxopentan-2-ylamino)-5-oxopentanoate), 4-isothiocyanatobenzenesulfonamide (0.171 g, 0.80 mmol) in acetonitrile (10 mL) containing DIPEA (0.40 mL) was stirred at room temperature under nitrogen for 48 h. The solvent was evaporated under reduced pressure to give a crude product, which was purified by flash chromatography 5% MeOH in DCM as eluent to give (S)-methyl 5-(4-iodobenzylamino)-4-((S)-5-methoxy-5-oxo-2-(3-(4-sulfamoylphenyl)thioureido)pentanamido)-5-oxopentanoate (0.469 g) as a white solid. MS (ESI), 756 (M+Na)+, 377 (M/2+H)+.

Workup

  1. customAfter the solvent was evaporated
  2. additionthe reaction mixture was diluted with DCM
  3. washwashed with sat. K2CO3
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0bec9c1cca1749829c0e56a370cd0d76
Source dataset
uspto-grants-2014_11
Patent number
US08877970B2

Reaction notes

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