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. 2012 Oct 29;51(44):11105-9.
doi: 10.1002/anie.201204400. Epub 2012 Sep 13.

Dissecting the influence of oxazolidinones and cyclic carbonates in sialic acid chemistry

Pavan K Kancharla  1 , Chandrasekhar Navuluri, David Crich
Affiliations

Dissecting the influence of oxazolidinones and cyclic carbonates in sialic acid chemistry

Pavan K Kancharla et al. Angew Chem Int Ed Engl. .

Abstract

At a moment's notice: Thermal equilibration of 1 and mass spectral analysis of sialyl phosphates suggest that the 4O,5N-oxazolidinone and the 4,5-O-carbonate systems influence the anomeric effect and the mechanisms of sialidation by virtue of their dipole moment in the mean plane of the pyranose ring. The electron-withdrawing effect destabilizes 2 and promotes associative glycosylation mechanisms. TEMPO = 2,2,6,6-tetramethylpiperidine N-oxide.

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Figures

Figure 1
Figure 1
Dipole moments (Debye units) of open chain and cyclic carbonyl functionalities in non-polar solvents
Figure 2
Figure 2
Orientations of the key O4 and N5 protecting group carbonyl dipole moments in the TEMPO sialosides (Side chains omitted for clarity)
Figure 3
Figure 3
Conformationally related 2-sialyl oxocarbenium ion 11 and radical 12
Figure 4
Figure 4
Onset cone voltages for fragmentation of sialyl phosphates
Figure 5
Figure 5
Protecting group dipoles in relations to the oxocarbenium ion: a) acyclic; b) oxazolidinone or carbonate; and c) N-acetyl oxazolidinone protection. Side chains are omitted for clarity.
Scheme 1
Scheme 1
Preparation of the TEMPO sialoside 2
Scheme 2
Scheme 2
Equilibration via the persistent radical effect
Scheme 3
Scheme 3
Lack of influence of the oxazolidinone on the kinetic selectivity of the 2-sialyl radical
Scheme 4
Scheme 4
Conformational analysis of nucleophilic attack on the putative glycosyl oxocarbenium ion 11
Scheme 5
Scheme 5
Mass spectral fragmentation and adduct formation
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