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The syntheses of enantiomerically enriched halo sulfonates 1, 6, and 8 are described in the Supporting Information.
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The syntheses of enantiomerically enriched halo sulfonates 1, 6, and 8 are described in the Supporting Information.
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33
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77950380884
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The term enantiospecificity [e.s., eeproduct/ee starting material x 100, provides a convenient method of describing the conservation of configurational purity for the reaction
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starting material) x 100%] provides a convenient method of describing the conservation of configurational purity for the reaction.
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Hexafluoroisopropanol has been used in classic studies of solvolysis mechanisms; see
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The insensitivity of e.s. to the concentration of NaOAc can be interpreted as a sodium ion assisted ionization to a solvent separated ion pair which collapses to product. If dissociated ions are not formed, then the concentration of NaOAc is irrelevant. For detailed discussion of solvolysis reactions, see:, Szwarc, M, Ed, John Wiley and Sons: New York, Chapter 3
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77950400550
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To determine if the bromonium ion transfer is associative or dissociative, acetolysis of (2R,3S)-610 was carried out in the presence of 4. The crossover product 5a was formed in 51:49 er. This outcome is ambiguous and cannot distinguish the pathways; see ref 5c
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10 was carried out in the presence of 4. The crossover product 5a was formed in 51:49 er. This outcome is ambiguous and cannot distinguish the pathways; see ref 5c.
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