The stereoselectivities of tributyltin hydride-mediated reductions of 5-bromo-D-glucuronides to L-iduronides are dependent on the anomeric substituent: syntheses and DFT calculations

Organic & Biomolecular Chemistry
Shifaza MohamedVito Ferro

Abstract

One of the shortest synthetic routes to L-iduronic acid derivatives is via free radical reduction of the C-5 bromide of the corresponding protected D-glucuronic acid derivative. The epimerization of such C-5 bromides to the L-ido derivatives via reaction with tributyltin hydride was investigated. It was found that the stereoselectivity of the reaction was dependent on the anomeric substituent. If the substituent was fluoride the L-ido product was obtained exclusively in 65-72% yield whereas the O-methyl or O-acetyl derivatives led to isomeric mixtures of both the L-ido and D-gluco products in different ratios depending on the reaction conditions. DFT calculations were performed to determine the stereoelectronic factors that favour formation of the L-ido isomer from the fluoride and suggest the selectivity is due to a transition state gauche effect and an Sn-F interaction.

References

Jan 1, 1991·Advances in Carbohydrate Chemistry and Biochemistry·L Somsák, R J Ferrier
Feb 12, 2002·Advances in Carbohydrate Chemistry and Biochemistry·B Casu, U Lindahl
Jul 26, 2002·Natural Product Reports·Dallas L Rabenstein
Nov 16, 2002·Carbohydrate Research·Yuriko Y RootPeter Norris
Dec 20, 2002·Angewandte Chemie·Ishan Capila, Robert J Linhardt
Jan 15, 2004·Journal of the American Chemical Society·Jinq-Chyi LeeShang-Cheng Hung
Jun 3, 2005·Chemical & Pharmaceutical Bulletin·Rika NakajimaHiroyuki Akita
Jul 14, 2005·Chemical Reviews·John M Whitelock, Renato V Iozzo
Oct 8, 2005·Journal of Computational Chemistry·Jay L BanksRonald M Levy
Jun 28, 2007·Chemical Communications : Chem Comm·Emiliano GemmaDusan Uhrín
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Dec 7, 2011·Organic & Biomolecular Chemistry·Shang-Cheng HungYong-Qing Zhong
Jul 17, 2012·Advances in Carbohydrate Chemistry and Biochemistry·Steven B Dulaney, Xuefei Huang
Feb 28, 2013·The FEBS Journal·Martin A ThelinAnders Malmstrom
Feb 28, 2013·Chemical Communications : Chem Comm·Medel Manuel L ZuluetaShang-Cheng Hung
Nov 5, 2013·Current Opinion in Chemical Biology·Medel Manuel L ZuluetaShang-Cheng Hung
Mar 13, 2014·Annual Review of Biochemistry·Ding Xu, Jeffrey D Esko
Aug 5, 2014·Carbohydrate Research·Benito CasuGiangiacomo Torri
Apr 22, 2015·Chemical Reviews·Tobias Gylling FrihedChristian Marcus Pedersen
Nov 29, 2015·Advances in Carbohydrate Chemistry and Biochemistry·Shifaza Mohamed, Vito Ferro

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Citations

Jun 3, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Ankita Paul, Suvarn S Kulkarni

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