Triethylamine → HCID 86732160, compound

HRID 930334Notes

Reaction equation

HRID 930334 reaction equation
FC(F)(F)S(O[C:7]1[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH:8]=1)(=O)=O.[CH:22]1([C:25]#[CH:26])[CH2:24][CH2:23]1.C(N(CC)CC)C>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].[Cu]I>[CH:22]1([C:25]#[C:26][C:7]2[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH:8]=2)[CH2:24][CH2:23]1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 138823CyclopropylacetyleneHCID 10991161Tert-butyl 4-(trifluoromethanesulfonyloxy)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 86732160HCID 86732160, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolvent

Procedure

A RT mixture of tert-butyl 4-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate (0.750 g, 2.264 mmol), trans-dichlorobis(triphenylphosphine)palladium (II) (0.081 g, 0.115 mmol) and copper (I) iodide (0.023 g, 0.121 mmol) in toluene (10 mL) was bubbled with argon for 15 min. cyclopropylacetylene (0.600 ml, 7.08 mmol, Aldrich) and triethylamine (0.350 ml, 2.52 mmol) were added resulting in a brown mixture after 5 min. The reaction mixture was partitioned between CH2Cl2/water and the aqueous layer was extracted with CH2Cl2 (3×). The combined organic layers were washed with brine and dried over MgSO4. The solution was filtered and the filtrate was evaporated onto silica gel and purified by flash chromatography (Isco (80 gram)) eluting with (EtOAc):hexanes (0:1→1:9) to give tert-butyl 4-(cyclopropylethynyl)-5,6-dihydropyridine-1(2H)-carboxylate as a yellow tar (344 mg, 61%). MS m/z=192 [M+H-tBu]+. Calculated for C11H13NO2: 191

Workup

  1. additionwere added
  2. customresulting in a brown mixture after 5 min
  3. customThe reaction mixture was partitioned between CH2Cl2/water
  4. extractionthe aqueous layer was extracted with CH2Cl2 (3×)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationThe solution was filtered
  8. customthe filtrate was evaporated onto silica gel
  9. custompurified by flash chromatography (Isco (80 gram))
  10. washeluting with (EtOAc)

Sources & evidence

ORD record
ord-02887cfb6c584f4fabe8b36aedf30fd3
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

Loading…