2021
DOI: 10.1021/acs.orglett.1c00551
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1,2-trans-Stereoselective Synthesis of C-Glycosides of 2-Deoxy-2-amino-sugars Involving Glycosyl Radicals

Abstract: We report for the first time that the imidate radical can be efficiently added to glycals to generate glycosyl radicals, based on which a general, toxic-reagent-free synthesis of C-glycosides of 2-deoxy-2-amino sugars has been developed. Complementary to previous strategies, the reaction is 1,2-trans-stereoselective and could use aryl alkenes as substrates. The late-stage functionalization and density functional theory calculations are reported.

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Cited by 25 publications
(11 citation statements)
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“…The good functional group tolerance renders significant strategies for the chemoselective biomolecule modification. In recent years, a series of C ‐glycosylation strategies have been reported [13a–f] . Notably, in the reactions, the stereoselectivity of the C ‐glycosylation was dominantly determined by the conformation of the glycosyl radical intermediate [13h–k] .…”
Section: Methodsmentioning
confidence: 99%
“…The good functional group tolerance renders significant strategies for the chemoselective biomolecule modification. In recent years, a series of C ‐glycosylation strategies have been reported [13a–f] . Notably, in the reactions, the stereoselectivity of the C ‐glycosylation was dominantly determined by the conformation of the glycosyl radical intermediate [13h–k] .…”
Section: Methodsmentioning
confidence: 99%
“…Same group in 2021, published first time a method for 1,2-trans-stereoselective construction of 2-deoxy-2-amino sugars enabled by iridium catalyst without using toxic reagents (Scheme 18). [68] In this protocol, an excited state of the photocatalyst generated an imidate radical, which intercepts with a double bond of glycal to form a glycosyl radical. Addition of aryl alkenes partners to glycosyl radical forging C-alkyl glycosides of 2-DASs.…”
Section: Iridium Based Photocatalysismentioning
confidence: 99%
“…Same group in 2021, published first time a method for 1,2‐ trans ‐stereoselective construction of 2‐deoxy‐2‐amino sugars enabled by iridium catalyst without using toxic reagents (Scheme 18). [68] …”
Section: Single Photoredox Catalysismentioning
confidence: 99%
“…[46] Imidate glycal derivatives 14 were reacted with styrenes or electron-deficient alkenes 15 in the presence of [Ir(dtbpy)(ppy) 2 ](PF 6 ) photocatalyst and an excess of iPr 2 NEt under blue light irradiation to give the C-alkyl 2-amino-2-deoxy glycosides 16 (Scheme 5). [47] This photocatalytic strategy provides a more sustainable alternative to classical radical methods, that generally require the use of stoichiometric toxic tin reagents and glycosyl selenides. [48,49] Under these reaction conditions, d-glucal and d-galactal derived imidates reacted to give the corresponding 1,2-trans glycosides in high yields and exclusive α-selectivity, while β-glycosides were obtained from d-allal derivatives.…”
Section: Direct Radical Additions To Unsaturated Sugarsmentioning
confidence: 99%