Acetone → (R)-6-[(1R,4aR,5S,8aR)-5-(tert-Butyl-dimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-2-methyl-hept-3-yn-2-ol

HRID 581611Notes

Reaction equation

HRID 581611 reaction equation
[C:1]([Si:5]([O:8][C@@H:9]1[C@H:18]2[C@@:13]([CH3:26])([C@@H:14]([C@H:19]([CH3:25])[CH2:20][CH:21]=[C:22](Br)Br)[CH2:15][CH2:16][CH2:17]2)[CH2:12][CH2:11][CH2:10]1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.[CH3:32][C:33]([CH3:35])=[O:34].[C-]#[C-]>C1COCC1>[C:1]([Si:5]([CH3:7])([CH3:6])[O:8][C@H:9]1[CH2:10][CH2:11][CH2:12][C@@:13]2([CH3:26])[C@H:18]1[CH2:17][CH2:16][CH2:15][C@@H:14]2[C@H:19]([CH3:25])[CH2:20][C:21]#[C:22][C:33]([CH3:35])([OH:34])[CH3:32])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 180AcetoneHCID 57092465tert-butyl-[(1S,4aR,5R,8aR)-5-((R)-4,4-dibromo-1-methyl-but-3-enyl)-4a-methyl-decahydro-naphthalen-1-yloxy]-dimethyl-silaneHCID 178418339ButyllithiumHCID 178420940HCID 178420940, compound

Product 1

HCID 57089693(R)-6-[(1R,4aR,5S,8aR)-5-(tert-Butyl-dimethyl-silanyloxy)-8a-methyl-decahydro-naphthalen-1-yl]-2-methyl-hept-3-yn-2-olYield 79.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

3.05 g (6.00 mmol) of tert-butyl-[(1S,4aR,5R,8aR)-5-((R)-4,4-dibromo-1-methyl-but-3-enyl)-4a-methyl-decahydro-naphthalen-1-yloxy]-dimethyl-silane was dissolved in 35 ml of abs. THF and cooled down to -78°. 11.6 ml of nBuLi (1.55M, hexane) was slowly added and the temperature maintained for 1 h. 2.15 ml (29.3 mmol) of acetone, dissolved in 5 ml of abs. THF, was then added to the resultant acetylide-solution and allowed to react for 30 minutes. The reaction was quenched by pouring onto crushed ice/NH4Cl, extracted twice with ether, washed with water and brine, dried over sodium sulfate and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=9/1) yielded 1.93 g of the title compound as colorless oil.

Workup

  1. temperaturethe temperature maintained for 1 h
  2. customto react for 30 minutes
  3. customThe reaction was quenched
  4. additionby pouring
  5. customonto crushed ice/NH4Cl
  6. extractionextracted twice with ether
  7. washwashed with water and brine
  8. dry with materialdried over sodium sulfate
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-f18eb33321a245d99d7f6a531c03f18b
Source dataset
uspto-grants-1999_07
Patent number
US05919986

Reaction notes

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