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| - Dual Activation in Asymmetric Allylsilane Addition to ChiralN-Acylhydrazones: Method Development, Mechanistic Studies, andElaboration of Homoallylic Amine Adducts
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| - Chiral N-acylhydrazones derived from commercially available 4-benzyl-2-oxazolidinone provide a rigid,conformationally restricted template to impart facial selectivity in additions to CN bonds. In the presenceof indium(III) trifluoromethanesulfonate [In(OTf)3], N-acylhydrazones undergo highly diastereoselectivefluoride-initiated additions of allylsilanes (aza-Sakurai reaction). Mechanistic studies including controlexperiments and comparisons with allyltributylstannane, allylmagnesium bromide, and allylindium speciesimplicate a dual activation mechanism involving addition of an allylfluorosilicate species to a chelateformed from In(OTf)3 and the chiral N-acylhydrazone. The N−N bonds of the adducts are readily cleavedin a two-step protocol to provide synthetically useful homoallylic N-trifluoroacetamides. Further elaborationof the latter compounds through Wacker oxidation and olefin metathesis provides diversely functionalizedbuilding blocks and expands the potential applications of this C−C bond construction approach toasymmetric amine synthesis.
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