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21st August 2013 @ 13:56

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Reaction information

*#Reaction file  
CSrxnsScheme_170.cdx
*Reaction file type CDX
*Procedure  n-BuLi (0.80 mL of a 2.5 M solution in hexanes, 1.0 mmol) was added dropwise to a solution of Cp2ZrCl2 (293 mg, 1.0 mmol) in dry THF (5.0 mL) at −78 °C. (Z)-4,4-bis(methoxymethyl)nona-1,6-diene (190 mg, 0.90 mmol) in dry THF (3.0 mL) was added dropwise to the reaction mixture at −78 °C.  After stirring at −78 °C for 20 mins the reaction mixture was warmed to room temperature.  After stirring at room temperature for 3 h the reaction mixture was cooled to −78 °C. Chloromethyl(dimethyl)phenylsilane (0.18 mL, 1 mmol) was added dropwise.  LiTMP [prepared by adding n-BuLi (0.40 mL of a 2.5 M solution in hexanes, 1.0 mmol) to a solution of 2,2,6,6-tetramethylpiperidine (0.17 mL, 1.0 mmol) in THF (1.0 mL) at 0 °C and stirring at 0 °C for 30 mins] was added dropwise at −78 °C.  After stirring at −78 °C for 45 mins the reaction mixture was stirred at room temperature for 30 mins.  MeOH (5.0 mL) and sat. aq. NaHCO3 solution (5.0 mL) were added and the reaction mixture stirred at room temperature for 16 h.  The reaction mixture was poured into water (100 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed sequentially with water (100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the intermediate silane as a yellow oil (381 mg). NMP (2.0 mL) was added to KH (642 mg of a 25–35% suspension in mineral oil, washed with hexane (3 × 5 mL), 4.0 mmol).  The reaction mixture was cooled to 0 °C. t-Butylhydroperoxide (1.10 mL, 4.0 mmol) was added and the reaction mixture warmed to room temperature.  The intermediate silane (240 mg, 0.66 mmol) in NMP (3.0 mL) was added and the reaction mixture stirred at room temperature for 10 mins.  TBAF (1.50 mL of a 1.0 M solution in THF, 1.5 mmol) was added and the reaction mixture heated to 70 °C for 15 h.  Na2S2O3 (150 mg) and water (5 mL) were added and the reaction mixture stirred for 5 mins.  The reaction mixture was extracted with ether (3 × 10 mL).  The organic extracts were combined, washed sequentially with water (2 × 25 mL), 2 M aq. NaOH solution (25 mL) and brine (25 mL­), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product as a yellow oil (273 mg).  Purification by column chromatography (SiO2, hexane/ether 1:2) gave the title compound as a colourless oil (72.7 mg, 45% over 2 steps).
*Yield (%)  45
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp119.pdf
AH Thesis_2011_pp224-250.pdf
Further information  Compound 170: 2-(4,4-Bis(methoxymethyl)-2-propylcyclopentyl)ethanol

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Attached Files
CSrxnsScheme_170.cdx
AH Thesis_2011_pp119.pdf
AH Thesis_2011_pp224-250.pdf