Triethyl phosphonoacetate → HCID 67216361, compound

HRID 1969899Notes

Reaction equation

HRID 1969899 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[CH2:17]([C@H:19]1[C@@H:23]([C:24]2[N:28]3[C:29]4[CH:35]=[CH:34][N:33]([S:36]([C:39]5[CH:45]=[CH:44][C:42]([CH3:43])=[CH:41][CH:40]=5)(=[O:38])=[O:37])[C:30]=4[N:31]=[CH:32][C:27]3=[N:26][N:25]=2)[CH2:22][C:21](=O)[CH2:20]1)[CH3:18].C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[CH2:17]([C@H:19]1[C@@H:23]([C:24]2[N:28]3[C:29]4[CH:35]=[CH:34][N:33]([S:36]([C:39]5[CH:40]=[CH:41][C:42]([CH3:43])=[CH:44][CH:45]=5)(=[O:37])=[O:38])[C:30]=4[N:31]=[CH:32][C:27]3=[N:26][N:25]=2)[CH2:22][C:21](=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:20]1)[CH3:18]

Participants

7

Reactant 4

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 516892Sodium BicarbonateHCID 58557823HCID 58557823, compound

Product 1

HCID 67216361HCID 67216361, compoundYield 89.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a slurry of sodium hydride (0.227 g, 5.67 mmol, 60% dispersion in oil) in THF (30 mL) was added ethyl 2-(diethoxyphosphoryl)acetate (1.18 mL, 5.90 mmol). After about 30 min a solution of (cis)-3-ethyl-4-(6-tosyl-6H-pyrrolo[2,3-e][1,2,4]triazolo[4,3-a]pyrazin-1-yl)cyclopentanone (2.00 g, 4.72 mmol) in THF (1.0 mL) was added. After about 4 h EtOAc and sat NaHCO3 were added. The organic layer was separated concd in vacuo and purified by flash chromatography on silica gel eluting with 20-100% EtOAc in DCM to afford ethyl 2-((cis)-3-ethyl-4-(6-tosyl-6H-pyrrolo[2,3-e][1,2,4]triazolo[4,3-a]pyrazin-1-yl)cyclopentylidene)acetate (2.08 g, 89%): LC/MS (Table 1, Method c) Rt=2.52-2.56 min; MS m/z: 494 (M+H)+ as a mixture of diastereomers and ethyl 2-((cis)-3-ethyl-4-(6H-pyrrolo[2,3-e][1,2,4]triazolo[4,3-a]pyrazin-1-yl)cyclopentylidene)acetate (0.150 g, 9%), as a mixture of diastereomers: LC/MS (Table 1, Method a) Rt=1.85-1.89; MS m/z: 340 (M+H)+.

Workup

  1. additionwere added
  2. customThe organic layer was separated concd in vacuo
  3. custompurified by flash chromatography on silica gel eluting with 20-100% EtOAc in DCM

Sources & evidence

ORD record
ord-8bfd841cd3664b3ab19bee4b4619582d
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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