Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation

Nat Chem. 2017 Dec;9(12):1213-1221. doi: 10.1038/nchem.2835. Epub 2017 Aug 14.

Abstract

Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amination
  • Amines / chemical synthesis*
  • Amines / chemistry
  • Catalysis
  • Hydrogenation
  • Molecular Structure
  • Oxidation-Reduction
  • Polymers / chemistry*
  • Ruthenium / chemistry

Substances

  • Amines
  • Polymers
  • polyol
  • Ruthenium

Associated data

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