Diethyl (cyanomethyl)phosphonate → tert-Butyl {3-[2-cyanovinyl]cyclohexyl}carbamate

HRID 712037Notes

Reaction equation

HRID 712037 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[CH:18]([CH:20]1[CH2:25][CH2:24][CH2:23][CH:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH2:21]1)=O>O1CCCC1>[C:7]([CH:9]=[CH:18][CH:20]1[CH2:25][CH2:24][CH2:23][CH:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH2:21]1)#[N:8]

Participants

5

Reactant 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 86717490tert-Butyl N-(3-formylcyclohexyl)carbamate

Product 1

HCID 86717491tert-Butyl {3-[2-cyanovinyl]cyclohexyl}carbamate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To 1.0 M potassium tert-butoxide in THF (2.0 mL, 2.0 mmol) was added diethyl cyanomethylphosphonate (0.30 mL, 1.8 mmol) dropwise at 0° C. and the mixture was stirred at 0° C. for 1 h. A solution of tert-butyl (3-formylcyclohexyl)carbamate (0.30 g, 1.3 mmol) in tetrahydrofuran (9.3 mL) was added dropwise, then cooling bath was removed, and the mixture was stirred at room temperature overnight. The mixture was diluted with EtOAc, washed with water, concentrated and purified on silica gel column (eluting with 0-30% EtOAc in hexanes) to give the desired product as a mixture of cis- and trans-isomer mixtures (0.12 g, 36%). LCMS calculated for C14H22N2O2Na (M+Na)+: m/z=273.2. Found: 273.1.

Workup

  1. temperaturecooling bath
  2. customwas removed
  3. stirringthe mixture was stirred at room temperature overnight
  4. additionThe mixture was diluted with EtOAc
  5. washwashed with water
  6. concentrationconcentrated
  7. custompurified on silica gel column (eluting with 0-30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-a7ef6578c94145b298ec38ddc04e0045
Source dataset
uspto-grants-2015_11
Patent number
US09181271B2

Reaction notes

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