Stereoselective Ethynylation and Propargylation of Chiral Cyclic Nitrones: Application to the Synthesis of Glycomimetics

Sara García-Viñuales; Ignacio Delso; Pedro Merino; Tomás Tejero

doi:10.1055/s-0035-1562500

Synthesis, Table of Contents

Synthesis 2016; 48(19): 3339-3351
DOI: 10.1055/s-0035-1562500

paper

Stereoselective Ethynylation and Propargylation of Chiral Cyclic Nitrones: Application to the Synthesis of Glycomimetics

Sara García-Viñuales

^aLaboratorio de Síntesis Asimétrica, Departamento de Síntesis y Estructura de Biomoléculas, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza, CSIC, Campus San Francisco, 50009 Zaragoza, Aragón, Spain Email: ttejero@unizar.es

,

Ignacio Delso

^aLaboratorio de Síntesis Asimétrica, Departamento de Síntesis y Estructura de Biomoléculas, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza, CSIC, Campus San Francisco, 50009 Zaragoza, Aragón, Spain Email: ttejero@unizar.es

^bServicio de NMR, Centro de Química y Materiales de Aragón (CEQMA), Universidad de Zaragoza, CSIC, Campus San Francisco, 50009 Zaragoza, Aragón, Spain

,

Pedro Merino

^aLaboratorio de Síntesis Asimétrica, Departamento de Síntesis y Estructura de Biomoléculas, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza, CSIC, Campus San Francisco, 50009 Zaragoza, Aragón, Spain Email: ttejero@unizar.es

,

Tomás Tejero*

^aLaboratorio de Síntesis Asimétrica, Departamento de Síntesis y Estructura de Biomoléculas, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza, CSIC, Campus San Francisco, 50009 Zaragoza, Aragón, Spain Email: ttejero@unizar.es

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Abstract

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Dedicated to Prof. J. Normant on occasion of his 80^th birthday. Sadly, Prof. J. Normant passed away June 9.

Abstract

Ethynylation and propargylation of chiral nonracemic polyhydroxylated cyclic nitrones with Grignard reagents are efficient methods for preparing building blocks containing an alkyne moiety to be used in copper-catalyzed azide alkyne cycloaddition click chemistry. Whereas ethynylation takes place with excellent diastereoselectivity, propargylation afforded mixtures of diastereomers in some cases. The use of (trimethylsilyl)propargyl bromide as precursor of the Grignard reagent is necessary to avoid the formation of undesired allene derivatives. DFT calculations explain, within the experimental error, the observed behavior. Cycloaddition of the obtained pyrrolidinyl alkynes with sugar azides derived from β-(1,3)-glucans provides glycomimetics suitable to be used against fungal transglycosylases.

Key words

nitrones - glycomimetics - propargylation - ethynylation - alkynes

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References

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Supplementary Material

Supporting Information