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21st August 2013 @ 15:47

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Reaction information

*#Reaction file  
*Reaction file type CDX
*Procedure  

General procedure F (see below) with diene 166 (4,4-bis(methoxymethyl)hepta-1,6-diene) (184 mg, 1.0 mmol), diethyl (chloromethyl)phosphonate (0.20 mL, 1.0 mmol), butyl isonitrile (0.1 mL, 1.0 mmol), nonanal (0.34 mL, 2.0 mmol) and BF3.OEt2  0.25 mL, 2.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 2:1) gave the title compound as an inseparable mixture of diastereoisomers (dr 1.3:1) as a pale yellow oil (33.9 mg, 9%).

 

 

General procedure F: elaboration of enamine 185:


n-BuLi (2 eq.) was added dropwise to a solution of Cp2ZrCl2 (1 eq.) in dry THF (5.0 mL per 1.0 mmol of Cp2ZrCl2) at −78 °C. A solution of diene 166 (1 eq.) in dry THF (3.0 mL per 1.0 mmol of diene 166) was added dropwise at −78 °C. The reaction mixture was warmed to room temperature and stirred for 2 h. The reaction mixture was cooled to −78 °C and the appropriate carbenoid precursor (1–1.3 eq.) and LDA (1–1.3 eq.) added sequentially. After stirring at −78 °C for 1 h the reaction mixture was warmed to −40 °C and the appropriate isonitrile (1 eq.) added. The reaction mixture was allowed to warm slowly to room temperature and stirred at this temperature for 16 h. The reaction mixture was cooled to −40 °C and the trapping reagent (1.5–2 eq.) was added. The reaction mixture was allowed to warm slowly to room temperature and stirred at this temperature for 16 h. 50% aq. HOAc solution (3 mL) was added to the reaction mixture followed by stirring at room temperature for 1 h. The reaction mixture was saturated with K2CO3, poured into water (100 mL) and extracted with ether (3 × 50 mL). The organic extracts were combined, washed sequentially with sat. aq. NaHCO3 (100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Yield (%)  9
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp137.pdf
AH Thesis_2011_pp224-250.pdf
Further information  Compound 189: 6-(1-Hydroxynonyl)-2,2-bis(methoxymethyl)hexahydro-1H-inden-5(6H)-one

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Overall reaction? True
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For step in multistep reaction - link to previous reaction step  
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Attached Files
AH Thesis_2011_pp137.pdf
AH Thesis_2011_pp224-250.pdf