Dichloromethane → 2-((1-(carboxymethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylic acid

HRID 77616Notes

Reaction equation

HRID 77616 reaction equation
C([O:5][C:6](=[O:69])[CH2:7][N:8]1[CH:12]=[CH:11][N:10]=[C:9]1[CH2:13][N:14]([CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][C:33](=[O:68])[NH:34][CH2:35][CH2:36][CH2:37][CH2:38][C@@H:39]([C:61]([O:63]C(C)(C)C)=[O:62])[NH:40][C:41](=[O:60])[NH:42][C@H:43]([C:53]([O:55]C(C)(C)C)=[O:54])[CH2:44][CH2:45][C:46]([O:48]C(C)(C)C)=[O:47])[CH2:15][C:16]([O:18]C(C)(C)C)=[O:17])(C)(C)C.C(Cl)Cl>C(O)(C(F)(F)F)=O>[C:6]([CH2:7][N:8]1[CH:12]=[CH:11][N:10]=[C:9]1[CH2:13][N:14]([CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][C:33](=[O:68])[NH:34][CH2:35][CH2:36][CH2:37][CH2:38][CH:39]([C:61]([OH:63])=[O:62])[NH:40][C:41](=[O:60])[NH:42][CH:43]([C:53]([OH:55])=[O:54])[CH2:44][CH2:45][C:46]([OH:48])=[O:47])[CH2:15][C:16]([OH:18])=[O:17])([OH:69])=[O:5]

Participants

4

Reactant 2

HCID 6344DichloromethaneHCID 59404265(19S,23S)-tetra-tert-butyl 2-((1-(2-tert-butoxy-2-oxoethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylate

Product 1

HCID 722748762-((1-(carboxymethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylic acid

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

[Re(CO)3][(19S,23S)-2-((1-(carboxymethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylic acid] (221). A solution of (19S,23S)-tetra-tert-butyl 2-((1-(2-tert-butoxy-2-oxoethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylate (18.8 mg, 0.019 mmol) in TFA (1.0 mL)/DCM (1.0 mL) was stirred at room temperature for overnight. The solvent was evaporated to give 19S,23S)-2-((1-(carboxymethyl)-1H-imidazol-2-yl)methyl)-13,21-dioxo-2,14,20,22-tetraazapentacosane-1,19,23,25-tetracarboxylic acid as a colorless oil. To a solution of the above deprotected product in water (1.0 mL) that was adjusted to pH=9 by 2 N NaOH was added Re(CO)3(H2O)OTf (0.50 mL, 0.10 mL/mmol). The reaction mixtures were stirred at room temperature for overnight and purified by HPLC to afford the title compound (4.0 mg, 19%) as a white solid. 1H NMR (400 MHz, DMSO-d6) 7.70 (t, J=5.6 Hz, 1H), 7.33 (s, 1H), 7.13 (s, 2H), 6.29 (d, J=8.4 Hz, 1H), 6.26 (d, J=8.4 Hz, 1H), 4.96 (d, J=4.8 Hz, 2H), 4.56 (d, J=16.4 Hz, 1H), 4.12 (d, J=16.8 Hz, 1H), 4.07-3.90 (m, 2H), 3.70 (d, J=17.2 Hz, 1H), 3.40 (d, J=17.2 Hz, 1H), 2.98-2.94 (m, 4H), 2.21 (q, J=7.73, 2H), 1.99 (t, J=7.6 Hz, 2H), 1.70-1.22 (m, 24H); MS (ESI), 485.2 (M/2+H)+.

Workup

  1. customThe solvent was evaporated

Sources & evidence

ORD record
ord-aee7cd9768f84e7190ccfe8bf3bed3bd
Source dataset
uspto-grants-2014_09
Patent number
US08840865B2

Reaction notes

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