Methyl iodide → HCID 86600185, compound

HRID 1829634Notes

Reaction equation

HRID 1829634 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[Li][CH2:8]CCC.[Si:12]([O:29][C@@H:30]1[CH2:47][CH2:46][C@@:45]2([CH3:48])[C@@H:32]([CH2:33][CH2:34][C@@H:35]3[C@@H:44]2[CH2:43][CH2:42][C@@:40]2([CH3:41])[C@H:36]3[CH2:37][CH2:38][C@@H:39]2[CH:49]=[O:50])[CH2:31]1)([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.IC>C1COCC1>[CH3:1][Si:2]([CH3:4])([CH3:3])[C:5]#[C:6][CH:49]([O:50][CH3:8])[C@H:39]1[CH2:38][CH2:37][C@H:36]2[C@H:35]3[C@H:44]([CH2:43][CH2:42][C@:40]12[CH3:41])[C@:45]1([CH3:48])[C@H:32]([CH2:31][C@H:30]([O:29][Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:47][CH2:46]1)[CH2:33][CH2:34]3

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 66111TrimethylsilylacetyleneHCID 86600183HCID 86600183, compoundHCID 178418339Butyllithium

Product 1

HCID 86600185HCID 86600185, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of trimethylsilylacetylene (0.066 mL, 0.48 mmol) in anhydrous THF (2 mL) at 0° C. was added a solution of n-BuLi (0.3 mL, 0.48 mmol) 1.6 M in hexanes and the resulting mixture was stirred for 2 h. Subsequently, the mixture was cooled to −78° C. and a solution of 3α-(t-butyldiphenylsilyloxy)-5α-androstan-17β-carboxaldehyde (90 mg, 0.16 mmol) in THF (2 mL) was added and the mixture was stirred at this temperature for 3 h after which iodomethane (0.1 mL, 1.6 mmol) was added and the resulting mixture was stirred at RT for 24 h. Quenching of the reaction by the addition of NH4Cl was followed by extraction with ethyl acetate. The organic layer was washed with water, brine, dried with (Na2SO4) and the solvent was evaporated in vacuo. Subsequent purification of the residue with flash column chromatography using petroleum ether/ethyl acetate 95/5 as eluent afforded the desired compound named above. Separation of the two epimers was accomplished with preparative thin layer chromatography using petroleum etherlacetone 98/2 as eluent.

Workup

  1. additionwas added
  2. stirringthe resulting mixture was stirred at RT for 24 h
  3. customQuenching of the reaction by the addition of NH4Cl
  4. extractionwas followed by extraction with ethyl acetate
  5. washThe organic layer was washed with water, brine
  6. dry with materialdried with (Na2SO4)
  7. customthe solvent was evaporated in vacuo
  8. customSubsequent purification of the residue with flash column chromatography

Sources & evidence

ORD record
ord-35591e035db548edb601b1e11552ec79
Source dataset
uspto-grants-2006_06
Patent number
US07064116B2

Reaction notes

Loading…