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Stereoretentive O-to-C Rearrangement Of Vinyl Acetals: Solvent Cage Effects As A Stereocontrol Element.

Y. Zhang, N. T. Reynolds, K. Manju, T. Rovis
Published 2002 · Chemistry, Medicine

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The Lewis acid-mediated rearrangement of chiral vinyl acetals may be induced to provide the product of stereoretention using Me3Al and BF3.OEt2 in concert. The selectivities obtained in this reaction (86:14 to 96:4) are complementary to that observed when relying on oxocarbenium facial bias to control the newly formed stereocenter. Evidence is presented that this reaction occurs by tight ion-pair binding in the solvent cage. The relay of C-O bond stereochemistry to a C-C bond stereocenter via ionic intermediates is an addition to similar established methods such as the Claisen rearrangement.

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