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Stabilization of Glucosyl Dioxolenium Ions by "Dual Participation" of the 2,2-Dimethyl-2-(ortho-nitrophenyl)acetyl (DMNPA) Protection Group for 1,2-cis-Glucosylation.
Remmerswaal, Wouter A; Houthuijs, Kas J; van de Ven, Roel; Elferink, Hidde; Hansen, Thomas; Berden, Giel; Overkleeft, Herman S; van der Marel, Gijsbert A; Rutjes, Floris P J T; Filippov, Dmitri V; Boltje, Thomas J; Martens, Jonathan; Oomens, Jos; Codée, Jeroen D C.
Afiliación
  • Remmerswaal WA; Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Houthuijs KJ; Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
  • van de Ven R; Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
  • Elferink H; Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
  • Hansen T; Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Berden G; Departament de Química Inorgànica i Orgànica & IQTUB, Universitat de Barcelona, 08028 Barcelona, Spain.
  • Overkleeft HS; Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
  • van der Marel GA; Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Rutjes FPJT; Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Filippov DV; Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
  • Boltje TJ; Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Martens J; Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
  • Oomens J; Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
  • Codée JDC; Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
J Org Chem ; 87(14): 9139-9147, 2022 07 15.
Article en En | MEDLINE | ID: mdl-35748115
ABSTRACT
The stereoselective introduction of glycosidic bonds is of paramount importance to oligosaccharide synthesis. Among the various chemical strategies to steer stereoselectivity, participation by either neighboring or distal acyl groups is used particularly often. Recently, the use of the 2,2-dimethyl-2-(ortho-nitrophenyl)acetyl (DMNPA) protection group was shown to offer enhanced stereoselective steering compared to other acyl groups. Here, we investigate the origin of the stereoselectivity induced by the DMNPA group through systematic glycosylation reactions and infrared ion spectroscopy (IRIS) combined with techniques such as isotopic labeling of the anomeric center and isomer population analysis. Our study indicates that the origin of the DMNPA stereoselectivity does not lie in the direct participation of the nitro moiety but in the formation of a dioxolenium ion that is strongly stabilized by the nitro group.
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Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Asunto principal: Glicósidos Idioma: En Revista: J Org Chem Año: 2022 Tipo del documento: Article País de afiliación: Países Bajos
Texto completo
Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Asunto principal: Glicósidos Idioma: En Revista: J Org Chem Año: 2022 Tipo del documento: Article País de afiliación: Países Bajos