Sodium Hydroxide → (2S,4S)-1-(tert-butoxycarbonyl)-4-cyanopyrrolidine-2-carboxylic acid

HRID 893055Notes

Reaction equation

C([O:3][C:4](=[O:19])[C@@H:5]1[CH2:9][C@H:8]([C:10]#[N:11])[CH2:7][N:6]1[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])C.[OH-].[Na+].C(O)(=O)C.O.[K+].[Br-]>CO>[C:15]([O:14][C:12]([N:6]1[CH2:7][C@@H:8]([C:10]#[N:11])[CH2:9][C@H:5]1[C:4]([OH:19])=[O:3])=[O:13])([CH3:18])([CH3:16])[CH3:17]

Participants

Conditions

Temperature: 22 °C

Procedure

The cyano ethyl ester (11a) from the previous experiment (2.9 g, 12.1 mmol) was dissolved in 100 mL methanol and 15 mL of 1M NaOH was added over five minutes with good stirring. This was allowed to stir for 16 h at 22° C. and was then treated with 1 mL of 80% acetic acid/water. This solution was then concentrated and worked-up according to method A. The residue crystallized on standing at 5° C., and was recrystallized from EtOAc/hexane to give 2.2 g (76% yield), m.p.=138°-139° C. (decomposition). IR (KBr) 2253 cm-1 (nitrile). 1H NMR δ 1.40/1.46 (2s, 9H), 2.44 (m, 1H), 2.70 (m, 1H), 3.12 (m, 1H), 3.65 (m, 1H), 3.92 (m, 1H), 4.36 (m, 1H). Anal. (C11H16N2O4), C, H, N. The X-ray crystal structure of this compound unambiguously confirmed the expected cis orientation of the nitrile with respect to the carboxylic acid.

Workup

concentrationThis solution was then concentrated
customThe residue crystallized
customon standing at 5° C.
customwas recrystallized from EtOAc/hexane
customto give 2.2 g (76% yield), m.p.=138°-139° C. (decomposition)

Sources & evidence

ORD record: ord-3d88c05b088a419f9a4cac8b2a14c37a
Source dataset: uspto-grants-1992_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05120859

Reaction notes

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