Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Asymmetric [2,3]-Wittig Rearrangements in the Presence of Sparteine Derivatives

  • Jahyo Kang (Department of Chemistry, Sogang University) ;
  • Won Oh Cho (Department of Chemistry, Sogang University) ;
  • Hyung Geun Cho (Department of Chemistry, Sogang University) ;
  • Hee Jin Oh (Department of Chemistry, Sogang University)
  • Published : 1994.09.20
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Abstract

Asymmetric [2,3]-Wittig rearrangements of allyl propargyl ethers in hexane were performed in the presence of s-butyllithium and (-)-${\alpha}$-isosparteine which is a $C_2$-symmetric chiral ligand for the alkyllithium reagent. The reactions of (Z)-or (E)-allyl 3-trimethylsilylpropargyl ethers at -78$^{\circ}C$ showed good diastereoselectivities (74-100%) and moderate enantioselectivities (29-71%). The absolute configurations of the rearrangement products were determined by the corresponding Mosher's esters. It was found that (-)-${\alpha}$ -isosparteine induced (R) configuration at the hydroxy carbon and syn stereochemistry more favorably. The possible transition state is discussed.

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References

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