Topic
Glycal
About: Glycal is a research topic. Over the lifetime, 897 publications have been published within this topic receiving 17422 citations.
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TL;DR: A sulfamate ester group was introduced at different positions of glycal to act as a nitrene source and, moreover, to allow the study of the relative reactivity of the nitrene transfer from different sites of the glycal molecule.
Abstract: We carried out a principle study on the reaction mechanism of rhodium-catalyzed intramolecular aziridination and aziridine ring opening at a sugar template. A sulfamate ester group was introduced at different positions of glycal to act as a nitrene source and, moreover, to allow the study of the relative reactivity of the nitrene transfer from different sites of the glycal molecule. The structural optimization of each intermediate along the reaction pathway was extensively done by using BPW91 functional. The crucial step in the reaction is the Rh-catalyzed nitrene transfer to the double bond of the glycal. We found that the reaction could proceed in a stepwise manner, whereby the N atom initially induced a single-bond formation with C1 on the triplet surface or in a single step through intersystem crossing (ISC) of the triplet excited state of the rhodium-nitrene transition state to the singlet ground state of the aziridine complexes. The relative reactivity for the conversion of the nitrene species to the aziridine obtained from the computed potential energy surface (PES) agrees well with the reaction time gained from experimental observation. The aziridine ring opening is a spontaneous process because the energy barrier for the formation of the transition state is very small and disappears in the solution calculations. The regio- and stereoselectivity of the reaction product is controlled by the electronic property of the anomeric carbon as well as the facial preference for the nitrene insertion, and the nucleophilic addition.
50 citations
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50 citations
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50 citations
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TL;DR: A new method for direct C2-aza-glycosylation with glycal donors has been developed, employing the new reagent combination of thianthrene-S-oxide and trifluoroacetic anhydride for glycal activation, in an overall one-pot procedure.
Abstract: Nitrogen transfer to glycals: A new method for direct C2-aza-glycosylation with glycal donors has been developed (see scheme), employing the new reagent combination of thianthrene-S-oxide and trifluoroacetic anhydride for glycal activation, in an overall one-pot procedure.
49 citations