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The 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.

The 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 Thumbnail


Authors

Markus Draskovits

Christian Stanetty

Marko D. Mihovilovic



Abstract

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.

Citation

Draskovits, M., Stanetty, C., Baxendale, I. R., & Mihovilovic, M. D. (2018). The 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(5), 2647-2659. https://doi.org/10.1021/acs.joc.7b03063

Journal Article Type Article
Acceptance Date Jan 25, 2018
Online Publication Date Jan 25, 2018
Publication Date Mar 2, 2018
Deposit Date Feb 1, 2018
Publicly Available Date Feb 16, 2018
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Electronic ISSN 1520-6904
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 83
Issue 5
Pages 2647-2659
DOI https://doi.org/10.1021/acs.joc.7b03063

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Publisher Licence URL
http://creativecommons.org/licenses/by/4.0/

Copyright Statement
Advance online version This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.





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