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A Substituent‐Directed Strategy for the Selective Synthesis of L‐Hexoses: An Expeditious Route to L‐Idose
Author(s) -
See Nicholas W.,
Wimmer Norbert,
Krenske Elizabeth H.,
Ferro Vito
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100042
Subject(s) - chemistry , substituent , stereoselectivity , anomer , yield (engineering) , selectivity , derivative (finance) , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , economics , financial economics , metallurgy , materials science
L‐Hexoses are rare but biologically significant components of various important biomolecules. However, most are prohibitively expensive (if commercially available) which limits their study and biotechnological exploitation. New, efficient methods to access L‐hexoses and their derivatives are thus of great interest. In a previous study, we showcased a stereoselective Bu 3 SnH‐mediated transformation of a 5‐ C ‐bromo‐D‐glucuronide to an L‐iduronide. We have now drawn inspiration from this result to derive a new methodology – one that can be harnessed to access other L‐hexoses. DFT calculations demonstrate that a combination of a β‐F at the anomeric position and a methoxycarbonyl substituent at C‐6 is key to optimising the selectivity for the L‐hexose product. Our investigations have also culminated in the development of the shortest known synthetic route to a derivative of L‐idose from a commercially available starting material (45 % yield over 3 steps). Collectively, these results address the profound lack of understanding of how to synthesise L‐hexoses in a stereoselective fashion.