530-25-6Relevant articles and documents
Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses - Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal
Draskovits, Markus,Stanetty, Christian,Baxendale, Ian R.,Mihovilovic, Marko D.
, p. 2647 - 2659 (2018)
The acyloxyallylation of unprotected aldoses was first demonstrated more than a decade ago as a potentially elegant two-carbon homologation of reducing sugars (upon ozonolysis); however, its application in real case syntheses remained scarce. Following up on such a successful showcase and to answer several pending questions about this attractive transformation, we engaged in an in depth methodological reinvestigation. The epimeric tetroses l-erythrose and d-threose in unprotected and protected form were successfully applied to the indium and also zinc-mediated acyloxyallylation, with the latter being a first for an unprotected sugar. The investigation largely benefited from the choice of these more exotic starting materials as it allowed unambiguous identification/quantification of the hexose-products which are available as authentic reference materials. The observed diastereoselectivities indicate a strong substrate control (stereochemistry at O2), and the influence of the reagent's structure on the selectivity was investigated in great detail. A strong facial diastereodivergence between related protected and unprotected structures was demonstrated and an unexpected, pronounced principle difference in performance between indium and zinc was revealed.
