Dimethyl Sulfide → HCID 19603849, compound

HRID 1604436Notes

Reaction equation

HRID 1604436 reaction equation
[CH3:1][C:2](=CC)[CH3:3].CSC.C#CC.Br[C:13]1[CH:14]=[C:15]([C:19]2[CH:24]=[CH:23][C:22]([CH:25]([CH3:30])[C:26]([O:28][CH3:29])=[O:27])=[CH:21][CH:20]=2)[CH:16]=[N:17][CH:18]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(CC)CC>C1COCC1.C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C(O)CC>[CH:1](/[C:13]1[CH:14]=[C:15]([C:19]2[CH:24]=[CH:23][C:22]([CH:25]([CH3:30])[C:26]([O:28][CH3:29])=[O:27])=[CH:21][CH:20]=2)[CH:16]=[N:17][CH:18]=1)=[CH:2]\[CH3:3]

Participants

12

Reactant 6

HCID 1068Dimethyl SulfideHCID 6335PropyneHCID 8021DiethylamineHCID 105532-Methyl-2-buteneHCID 11776TriphenylphosphineHCID 19603848HCID 19603848, compound

Product 1

HCID 19603849HCID 19603849, compoundYield 43.6%

Reagents, catalysts & solvents 5

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 10311-PropanolSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a 0° C. solution of 2-methyl-2-butene (2M in THF, 14 mL, 28 mmol) in THF (20 mL) was added BH3.DMS (10 M in DMS, 1.4 mL, 14 mmol). After 30 min, the solution was allowed to warm to room temperature for 1 h, then cooled to -40° C. A stream of propyne (large excess) was passed through the solution, and the solution was allowed to warm to 0° C., then concentrated. 14b (100 mg, 0.31 mmol), Pd2 (dba)3)(14 mg, 0.014 mmol) and triphenylphosphine (18 mg, 0.068 mmol) were added, and the mixture was dissolved in 20 mL of 3:1:1 toluene:nPrOH:water. Et2NH (0.5 mL, 4.8 mmol) was added, the solution was degassed, and heated to reflux for 3 h. The mixture was cooled and partitioned between EtOAc and saturated aqueous NH4Cl. The organic phase was washed with brine, dried over MgSO4 and evaporated. Purification by flash chromatography (20% EtOAc/hexanes to 40% EtOAc/hexanes) provided 38 mg of the title compound.

Workup

  1. temperaturecooled to -40° C
  2. temperatureto warm to 0° C.
  3. concentrationconcentrated
  4. customthe solution was degassed
  5. temperatureheated
  6. temperatureto reflux for 3 h
  7. temperatureThe mixture was cooled
  8. custompartitioned between EtOAc and saturated aqueous NH4Cl
  9. washThe organic phase was washed with brine
  10. dry with materialdried over MgSO4
  11. customevaporated
  12. customPurification by flash chromatography (20% EtOAc/hexanes to 40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-5d12188d108a49d9b2d3a7ca4717cf3b
Source dataset
uspto-grants-1999_11
Patent number
US05994379

Reaction notes

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