Iodine → [1-Cyano-2-(tetrahydro-pyran-4-yl)-hex-5-enyl]-phosphonic acid diethyl ester

HRID 506850Notes

Reaction equation

HRID 506850 reaction equation
II.Br[CH2:4][CH2:5][CH:6]=[CH2:7].[CH2:8]([O:10][P:11]([C:16]([C:24]#[N:25])=[CH:17][CH:18]1[CH2:23][CH2:22][O:21][CH2:20][CH2:19]1)(=[O:15])[O:12][CH2:13][CH3:14])[CH3:9].[NH4+].[Cl-]>C1COCC1.[Cu]I.C(OCC)(=O)C>[CH2:8]([O:10][P:11]([CH:16]([C:24]#[N:25])[CH:17]([CH:18]1[CH2:19][CH2:20][O:21][CH2:22][CH2:23]1)[CH2:7][CH2:6][CH:5]=[CH2:4])(=[O:15])[O:12][CH2:13][CH3:14])[CH3:9]

Participants

8

Reactant 4

HCID 807IodineHCID 21241Homoallyl bromideHCID 25517Ammonium ChlorideHCID 72481733[1-Cyano-2-(tetrahydro-pyran-4-yl)-vinyl]-phosphonic acid diethyl ester

Product 1

HCID 59428163[1-Cyano-2-(tetrahydro-pyran-4-yl)-hex-5-enyl]-phosphonic acid diethyl ester

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

In a flask, Mg (5.7 g) was placed in THF (50 mL) with an iodine chip. The reaction mixture was vigorously stirred and heated slightly, as 4-bromobutene (25 mL) was added. After consumption of Mg metal, the resulting solution was cannulated into a flask containing a mixture of [1-cyano-2-(tetrahydro-pyran-4-yl)-vinyl]-phosphonic acid diethyl ester (21.78 g, 79.7 mmol), prepared as described in Example 1 Step D above, and CuI (0.3 g) with THF (30 mL). The resulting mixture was stirred for three hours. Saturated aqueous NH4Cl solution and ethyl acetate were then added. The organic layer was separated and dried with MgSO4, filtered, and evaporated in vacuo to yield an oil.

Workup

  1. additionwas added
  2. customAfter consumption of Mg metal
  3. customthe resulting solution was cannulated into a flask
  4. additioncontaining
  5. customprepared
  6. stirringThe resulting mixture was stirred for three hours
  7. customThe organic layer was separated
  8. dry with materialdried with MgSO4
  9. filtrationfiltered
  10. customevaporated in vacuo
  11. customto yield an oil

Sources & evidence

ORD record
ord-683559c8c93d46d3a973bd7f23790b4f
Source dataset
uspto-grants-2010_08
Patent number
US07786116B2

Reaction notes

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