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21st August 2013 @ 15:43

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Reaction information

*#Reaction file  
CSrxnsScheme_186.cdx
*Reaction file type CDX
*Procedure

 General procedure F (see below) with diene 166 (4,4-bis(methoxymethyl)hepta-1,6-diene) (92.0 mg, 0.50 mmol), diethyl (chloromethyl)phosphonate (0.10 mL, 0.65 mmol), butyl isonitrile (0.07 mL, 0.65 mmol), benzaldehyde (0.10 mL, 1.0 mmol) and BF3.OEt2 (0.12 mL, 1.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 3:1) gave two diastereoisomers (dr 1:2) of the title compound.  The first diastereoisomer was obtained as a pale yellow oil (64.0 mg, 39%).

The second diastereoisomer was obtained as a pale yellow oil (33.6 mg, 20%).

 

 

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 (%)  39/20
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp134.pdf
AH Thesis_2011_pp224-250.pdf
Further information  Compound 186: 6-(Hydroxy(phenyl)methyl)-2,2-bis(methoxymethyl)hexahydro-1H-inden-5(6H)-one

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Overall reaction? True
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Attached Files
AH Thesis_2011_pp134.pdf
CSrxnsScheme_186.cdx
AH Thesis_2011_pp224-250.pdf