Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 85, Issue 7, Pages 4861-4880Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.0c00059
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Funding
- Ministerio de Economia y Competitividad [CTQ2010-18244]
- Fundacion CajaCanarias [2015-BIO08]
- Gobierno de Canarias [ProID2017010017]
- Ministerio de Economia y Competitividad
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The anomeric alkoxyl radical beta-fragmentation (ARF) of carbohydrates possessing an electron-withdrawing group (EWG) at C2, promoted by PhI(OAc)(2)/I-2, gives rise to an acyclic iodide through which a pentavalent atom of phosphorus can be introduced via the Arbuzov reaction. After selective hydrolysis and subsequent cyclization, the phosphonate or phosphinate intermediates can be converted into 2-deoxy-1-phosphahexopyranose and 2-deoxy-1-phosphapentopyranose sugars. The ARF of carbohydrates with an electron-donor group (EDG) at C2 proceeds by a radical-polar crossover mechanism, and the cyclization occurs by nucleophilic attack of a conveniently positioned phosphonate or phosphinate group to the transient oxocarbenium ion. This alternative methodology leads to 5-phosphasugars with a 4-deoxy-5-phosphapentopyranose framework. The structure and conformation of the 2-oxo-1,2-oxaphosphinane and 2-oxo-1,2-oxaphospholane ring systems in different carbohydrate models have been studied by NMR and X-ray crystallography.
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