Sodium Cyanide → Tert-butyl 1-(4-chlorophenyl)-2-cyanoethylcarbamate

HRID 423044Notes

Reaction equation

[C-:1]#[N:2].[Na+].CS(O[CH2:9][CH:10]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=1)(=O)=O>CN(C=O)C>[Cl:17][C:14]1[CH:15]=[CH:16][C:11]([CH:10]([NH:18][C:19](=[O:20])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])[CH2:9][C:1]#[N:2])=[CH:12][CH:13]=1

Participants

Conditions

Temperature: 80 °C

Procedure

Sodium cyanide (105 mg, 2.14 mmol) was added to 2-(tert-butoxycarbonylamino)-2-(4-chlorophenyl)ethyl methanesulfonate (Intermediate 23) (300 mg, 0.86 mmol) in DMF (5 mL) at 20° C. The resulting suspension was stirred at 80° C. for 3 hours. The reaction mixture was evaporated to dryness and redissolved in water (10 mL), and washed sequentially with DCM 3× (10 mL). The organic layer was dried over MgSO4, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 25% EtOAc in isohexane. Pure fractions were evaporated to dryness to afford tert-butyl 1-(4-chlorophenyl)-2-cyanoethylcarbamate (209 mg, 87%) as a white solid. 1H NMR (399.9 MHz, DMSO-d6) δ1.38-1.42 (9H, s), 2.82-2.89 (2H, m), 4.89 (1H, d), 7.38-7.45 (4H, m), 7.76 (1H, d). m/z (ESI+) (M−H)−=279; HPLC tR=2.42 min.

Workup

customThe reaction mixture was evaporated to dryness
dissolutionredissolved in water (10 mL)
washwashed sequentially with DCM 3× (10 mL)
dry with materialThe organic layer was dried over MgSO4
filtrationfiltered
customevaporated
customto afford crude product
customThe crude product was purified by flash silica chromatography, elution gradient 0 to 25% EtOAc in isohexane
customPure fractions were evaporated to dryness

Sources & evidence

ORD record: ord-9236046ba12149d58d07553a33dc672f
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101623B2

Reaction notes

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