Studies on the Mechanism and Origin of Stereoselective Opening of Chiral Dioxane Acetals

Scott E. Denmark, Neil G. Almstead

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A systematic examination of the mechanism and origin of stereoselection in the reaction of dioxane acetals with allyltrimethylsilane was undertaken. Experimental tests for two limiting mechanisms, synchronous (SN2-like) and dissociative (SNl-like) substitution processes, were investigated. The meso 2,4,6-trisubstituted 1,3-dioxane acetals cis- and trans-l provided an interesting opportunity to test the timing of bond breaking and making in the substitution reaction. The modest and C(2)-substituent-dependent selectivity excluded the possibility of a direct SN2-type attack on a complexed acetal. Further, the enol ethers 3 and 5 and acyclic acetal 7 were studied as precursors of the putative oxocarbenium ion intermediate in the dissociative limit. The weak and inverted selectivity observed with these substrates ruled out the intermediacy of the extended, separated ion in reactions of the cyclic acetals under similar conditions. A unified mechanistic scheme involving three distinct ion pairs is proposed to explain the dependence of allylation selectivity on structural and experimental variables. The three species are analogous to those proposed in the classic Winstein scheme: (1) an intimate ion pair, (2) an external ion pair, and (3) a separated ion. Each of these proposed intermediates has a different stereochemical profile and the ultimate outcome is a composite of those factors that balance the contribution of the different intermediates. The influence of C(2) substituent, acetal configuration, Lewis acid type and stoichiometry, allylsilane stoichiometry, concentration, solvent, and temperature were investigated and integrated in the proposed mechanistic scheme.

Original languageEnglish (US)
Pages (from-to)8089-8110
Number of pages22
JournalJournal of the American Chemical Society
Issue number21
StatePublished - Oct 1 1991

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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