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21st August 2013 @ 13:53

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Reaction information

*#Reaction file  
CSRxnsScheme_167.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. 4,4-bis(methoxymethyl)hepta-1,6-diene (170 mg, 0.92 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 2 h the reaction mixture was cooled to −78 °C. Chloromethyl(dimethyl)methoxysilane (0.15 mL, 1.1 mmol) was added dropwise.  LiTMP [prepared by adding n-BuLi (0.42 mL of a 2.5 M solution in hexanes, 1.1 mmol) to a solution of 2,2,6,6-tetramethylpiperidine (0.18 mL, 1.1 mmol) in THF (3.0 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 (313 mg).  KF (334 mg, 5.7 mmol), KHCO3 (360 mg, 3.6 mmol) and H2O2 (2 ml of a 30% solution in water, 20 mmol) were added to the intermediate silane (313 mg, 0.92 mmol) in MeOH (2.0 mL) and water (2.0 mL).  The reaction mixture was stirred at room temperature for 18 h.  5% Pd/C (200 mg, 94.0 mmol) was added to the reaction mixture.  The reaction mixture was filtered through celite and extracted with ether (2 × 20 mL).  The organic extracts were combined, washed with water (3 × 100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product as a yellow oil (136 mg).  Purification by column chromatography (SiO2, hexane/Et2O 1:1) gave the title compound as a colourless oil (70.4 mg, 33% over 2 steps).

*Yield (%)  33
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp117.pdf
AH Thesis_2011_pp176-223.pdf
Further information  Compound 167: 2-(4,4-Bis(methoxymethyl)-2-methylcyclopentyl)ethanol

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Overall reaction? True
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Attached Files
CSRxnsScheme_167.cdx
AH Thesis_2011_pp117.pdf
AH Thesis_2011_pp176-223.pdf