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Chemoselective conversion of biologically sourced polyols into chiral synthons

Nature Chemistry volume 7, pages 576–581 (2015)Cite this article

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An Erratum to this article was published on 20 August 2015

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Abstract

Crude oil currently provides much of the world's energy, but it is also the source of many feedstock chemicals. Methodology for the conversion of biomass into useful chemicals has often focused on either complete deoxygenation or the production of high-volume platform chemicals. Here, we describe the chemoselective partial reduction of silyl-protected C6O6-derived polyols to produce a diverse set of oxygen-functionalized chiral synthons. The combination of B(C6F5)3 and a tertiary silane efficiently generates a reactive equivalent of an electrophilic silylium ion (R3Si+) and a hydride (H−) reducing agent. The mechanism of oxygen loss does not involve a dehydrative elimination and thus avoids ablation of stereochemistry. Neighbouring group participation and the formation of cyclic intermediates is key to achieving selectivity in these reactions and, where both primary and secondary C–O bonds are present, the mechanism allows further control. The method provides—in one or two synthetic steps—highly improved syntheses of many C6On synthons as well as several previously undescribed products.

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Figure 1: BCF-catalysed reduction of C6O6 feedstocks.
Figure 2: Partial reduction of persilylated hexols gives a mixture of tetra- and trioxygenated products.
Figure 3: Evidence for the formation of cyclic intermediates in selective reduction.
Figure 4: Selective reduction of 1,2-deoxysugars.
Figure 5: Partial reduction of isosorbide and isomannide.

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Change history

  • 11 August 2015

    In the original graphical abstract for this Article, an in-house error meant that an incorrect intermediate was shown; this has now been corrected in the online versions.

  • 20 August 2015

    Nature Chemistry 7, 576–581 (2015); published online 23 June 2015; corrected after print 11 August 2015. In the original graphical abstract for this Article, an in-house error meant that an incorrect intermediate was shown; this has now been corrected in the online versions, and should have appearedas shown below.

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Acknowledgements

The authors acknowledge the Department of Energy (DE-FG02-05ER15630) for financial support.

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Author notes

  1. Laura L. Adduci and Trandon A. Bender: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, 27599, North Carolina, USA

    Laura L. Adduci, Trandon A. Bender, Jennifer A. Dabrowski & Michel R. Gagné

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  1. Laura L. Adduci
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  2. Trandon A. Bender
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Contributions

L.L.A., T.A.B. and M.R.G. conceived and designed the experiments. L.L.A., T.A.B. and J.A.D. performed the experiments. All co-authors participated in the process of data analysis and the writing of the paper.

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Correspondence to Michel R. Gagné.

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The authors declare no competing financial interests.

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Adduci, L., Bender, T., Dabrowski, J. et al. Chemoselective conversion of biologically sourced polyols into chiral synthons. Nature Chem 7, 576–581 (2015). https://doi.org/10.1038/nchem.2277

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