Chlorotrimethylsilane → HCID 9865535, compound

HRID 991869Notes

Reaction equation

HRID 991869 reaction equation
[CH3:1][Li].CN(C)P(N(C)C)(N(C)C)=O.[CH3:14][C:15]1[CH2:20][CH2:19][CH2:18][C:17](=[O:21])[C:16]=1[CH:22]=[CH:23][C:24]#[C:25][C:26]1[CH:36]=[CH:35][C:29]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[CH:28][CH:27]=1.Cl[Si:38]([CH3:41])([CH3:40])[CH3:39]>CSC.[Cu]Br.CCOCC.N1C=CC=CC=1.C1COCC1>[CH3:14][C:15]1([CH3:1])[C:16](/[CH:22]=[CH:23]/[C:24]#[C:25][C:26]2[CH:27]=[CH:28][C:29]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[CH:35][CH:36]=2)=[C:17]([O:21][Si:38]([CH3:41])([CH3:40])[CH3:39])[CH2:18][CH2:19][CH2:20]1

Participants

9

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 12679HexamethylphosphoramideHCID 56987556HCID 56987556, compound2×HCID 178418348HCID 178418348, compound

Product 1

HCID 9865535HCID 9865535, compound

Reagents, catalysts & solvents 4

HCID 2724234Bromo(thiobis(methane))copperCatalystHCID 1049PyridineSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

A 1.3 M solution of methyllithium (0.78 mL, 1.04 mmol) was added to a stirring suspension of copper (1) bromide-dimethyl sulfide (107 mg, 0.52 mmol) and 2 mL of THF at −78° C. The solution was warmed to −40° C. over 30 minuts and then re-cooled to −78° C. Freshly distilled hexamethylphosphoramide (0.091 mL, 0.52 mmol) was added, and the solution was stirred at −78° C. for 30 minutes. A solution of ethyl 4-(4-(2-methyl-6-oxocyclohex-1-enyl)but-3-en-1-ynyl)benzoate (Compound H, 80 mg, 0.26 mmol), chlorotrimethylsilane (0.07 mL, 3.94 mmol) and 2.5 mL of THF was added. After the solution was stirred at −78° C. for 1 hour, pyridine (0.020 mL) and ether (0.065 mL) were added. The reaction was then quenched by the addition of 5% aqueous NaHCO3. The layers were separated and the aqueous layer was extracted 3 times with ethyl acetate. The solvents were removed under reduced pressure, and the residue was purified by silica gel chromatography (10:1, hexane:ethyl acetate) to give the title compound as a yellow solid.

Workup

  1. temperaturere-cooled to −78° C
  2. stirringAfter the solution was stirred at −78° C. for 1 hour
  3. customThe reaction was then quenched by the addition of 5% aqueous NaHCO3
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted 3 times with ethyl acetate
  6. customThe solvents were removed under reduced pressure
  7. customthe residue was purified by silica gel chromatography (10:1, hexane:ethyl acetate)

Sources & evidence

ORD record
ord-3a08f8496eab46a687c196afc8cf45fc
Source dataset
uspto-grants-2002_10
Patent number
US06465646B1

Reaction notes

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