Sodium Azide → 1,1-Dimethylethyl (2S)-2-[6-(2-azidoacetyl)-1H-benzimidazol-2-yl]-1-pyrrolidinecarboxylate

HRID 1945353Notes

Reaction equation

[N-:1]=[N+:2]=[N-:3].[Na+].Cl[CH2:6][C:7]([C:9]1[CH:10]=[CH:11][C:12]2[N:16]=[C:15]([C@@H:17]3[CH2:21][CH2:20][CH2:19][N:18]3[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[NH:14][C:13]=2[CH:29]=1)=[O:8]>C(#N)C>[N:1]([CH2:6][C:7]([C:9]1[CH:10]=[CH:11][C:12]2[N:16]=[C:15]([C@@H:17]3[CH2:21][CH2:20][CH2:19][N:18]3[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[NH:14][C:13]=2[CH:29]=1)=[O:8])=[N+:2]=[N-:3]

Participants

Conditions

Temperature: 60 °C

Procedure

Sodium azide (1.79 g, 27.48 mmol) was added in one portion to a solution of J.30 (5)-tert-butyl 2-(6-(2-chloroacetyl)-1H-benzo[d]imidazol-2-yl)pyrrolidine-1-carboxylate (10.0 g, 27.48 mmol) in acetonitrile (200 mL) and stirred at 60° C. for 16 h. The reaction mixture was concentrated to ⅕ volume, diluted with ethyl acetate, and washed with water and brine prior to being dried (Na2SO4). Concentration gave J.31 (S)-tert-butyl 2-(6-(2-azidoacetyl)-1H-benzo[d]imidazol-2-yl)pyrrolidine-1-carboxylate 6.8 g (48%) as a golden orange foam. 1H NMR (500 MHz, DMSO-d6) δ: 8.22/8.03 (s, 1H), 7.80-7.75 (m, 1H), 7.65/7.56 (d, J=8.5 Hz, 1H), 4.99-4.93 (m, 3H), 3.60 (br. s, 1H), 3.46-3.41 (m, 1H), 2.38-2.27 (m, 1H), 2.01-1.89 (m, 3H), 1.40/1.06 (s, 9H). LC (Cond.-D2): 1.97 min; LC/MS: Anal. Calcd. for [M+H]+ C18H23N6O3: 371.19; found: 371.32. HRMS: Anal. Calcd. for [M+H]+ C18H23N6O3: 371.1832; found: 371.1825.

Workup

concentrationThe reaction mixture was concentrated
additiondiluted with ethyl acetate
washwashed with water and brine
dry with materialto being dried (Na2SO4)
concentrationConcentration

Sources & evidence

ORD record: ord-e3862646f6a840fea243520c8ff6134b
Source dataset: uspto-grants-2013_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08394968B2

Reaction notes

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