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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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References

    1. Fraser-Reid B, Lopez C. Top. Curr. Chem. 2011;301:1–30. - PubMed
    2. Gomez AM. Top. Curr. Chem. 2011;301:31–68. - PubMed
    3. Shiao TC, Roy R. Top. Curr. Chem. 2011;301:69–108. - PubMed
    4. Kim KS, Suk D-H. Top. Curr. Chem. 2011;301:109–140. - PubMed
    5. Aubry S, Sasaki K, Sharma I, Crich D. Top. Curr. Chem. 2011;301:141–188. - PubMed
    6. Premathilake HD, Demchenko AV. Top. Curr. Chem. 2011;301:189–222. - PMC - PubMed
    7. Wu C-Y, Wong C-H. Top. Curr. Chem. 2011;301:223–252. - PubMed
    8. Codée JDC, Christina AE, Walvoort MTC, Overkleeft HS, van der Marel GA. Top. Curr. Chem. 2011;301:253–290. - PubMed
    1. Codée JDC, Ali A, Overkleeft HS, van der Marel GA. CR Chimie. 2011;14:178–193.
    2. Litjens REJN, van den Bos LJ, Codée JDC, Overkleeft HS, van der Marel G. Carbohydr. Res. 2007;342:419–429. - PubMed
    1. Crich D, Vinod AU. J. Org. Chem. 2005;70:1291–1296. - PubMed
    2. Manabe S, Ishii K, Ito Y. J. Am. Chem. Soc. 2006;128:10666–10667. - PubMed
    3. Kerns RJ, Zha C, Benakli K, Liang Y-Z. Tetrahedron Lett. 2003;44:8069–8072.
    4. Olsson JDM, Eriksson L, Lahmann M, Oscarson S. J. Org. Chem. 2008;73:7181–7188. - PubMed
    5. Satoh H, Manabe S, Ito Y, Luthi HP, Laino T, Hutter J. J. Am. Chem. Soc. 2011;133:5610–5619. - PubMed
    1. Tanaka H, Nishiura Y, Takahashi T. J. Am. Chem. Soc. 2006;128:7124–7125. - PubMed
    2. Farris MD, De Meo C. Tetrahedron Lett. 2007;48:1225–1227.
    3. Crich D, Li W. J. Org. Chem. 2007;72:2387–2391. - PMC - PubMed
    4. Crich D, Li W. J. Org. Chem. 2007;72:7794–7797. - PMC - PubMed
    5. Crich D, Wu B. Org. Lett. 2008;10:4033–4035. - PMC - PubMed
    6. Hsu C-H, Chu K-C, Lin Y-S, Han J-L, Peng Y-S, Ren C-T, Wu C-Y, Wong C-H. Chem. Eur. J. 2010;16:1754–1760. - PubMed
    7. Chu K-C, Ren C-T, Lu C-P, Hsu C-H, Sun T-H, Han J-L, Pal B, Chao T-A, Lin Y-F, Wu S-H, Wong C-H, Wu C-Y. Angew. Chem. Int. Ed. 2011;50:9391–9395. - PubMed
    8. Harris BN, Patel PP, Gobble CP, Stark MJ, De Meo C. Eur. J. Org. Chem. 2011:4023–4027.
    9. Wang Y-J, Jia J, Gu Z-Y, Liang F-F, Li R-C, Huang M-H, Xu C-S, Zhang J-X, Men Y, Xing G-W. Carbohydr. Res. 2011;346:1271–1276. - PubMed
    10. Crich D, Navuluri C. Angew. Chem. Int. Ed. 2010;49:3049–3052. - PMC - PubMed
    11. Gu Z.-y., Zhang J.-x., Guo-wen Xing G.-x. Chem. Asian J. 2012;7:1524–1528. - PubMed
    1. Noel A, Delpech B, Crich D. Org. Lett. 2012;14:1342–1345. - PubMed

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