[Back]

M. Draskovits, C. Stanetty, I. Baxendale, M.D. Mihovilovic:
"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";
Journal of Organic Chemistry, 83 (2018), 5; 2647 - 2659.

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.

http://dx.doi.org/10.1021/acs.joc.7b03063

https://publik.tuwien.ac.at/files/publik_273441.pdf