Diethyl (cyanomethyl)phosphonate → HCID 67451704, compound

HRID 1853059Notes

Reaction equation

[C:1]([CH2:3]P(=O)(OCC)OCC)#[N:2].CC([O-])(C)C.[K+].O=[C:19]1[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20]1>C1COCC1>[C:1]([CH:3]=[C:19]1[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20]1)#[N:2]

Participants

Conditions

Temperature: 0 °C

Procedure

Diethyl cyanomethylphosphonate (4.247 mL, 26.99 mmol) was suspended in THF (135.0 mL) and cooled to 0° C. Potassium 2-methylpropan-2-olate (32.39 mL, 32.39 mmol) was added portion-wise and stirred at 0° C. for 10 minutes. tert-Butyl 3-oxopyrrolidine-1-carboxylate (5 g, 26.99 mmol) was added dropwise as a solution in THF (25 mL). The resulting mixture was allowed to warm to ambient temperature overnight. The reaction mixture was concentrated under reduced pressure and the residue partitioned between saturated aqueous NH4Cl and EtOAc. The organics were washed with brine, dried, MgSO4 and concentrated under reduced pressure to afford the crude material, which was passed through a pad of Celite® and silica, eluting with DCM to furnish tert-butyl 3-(cyanomethylene)pyrrolidine-1-carboxylate (2.5 g, 12.00 mmol, 44.47% yield. 1H NMR (CDCl3) δ 5.8 (s, 1H), 4.26 (t, 2H), 3.85 (s, 2H), 2.28 (t, 2H), 2.06-1.96 (m, 1H), 1.54 (s, 9H).

Workup

temperatureto warm to ambient temperature overnight
concentrationThe reaction mixture was concentrated under reduced pressure
customthe residue partitioned between saturated aqueous NH4Cl and EtOAc
washThe organics were washed with brine
customdried
concentrationMgSO4 and concentrated under reduced pressure
customto afford the crude material, which
washeluting with DCM

Sources & evidence

ORD record: ord-07f845d903f44fa7accefaf3f6df0999
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962596B2

Reaction notes

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