Titanium-beta zeolites catalyze the stereospecific isomerization of d -glucose to l -sorbose via intramolecular C5-C1 hydride shift

  • Gounder R
  • Davis M
  • 25

    Readers

    Mendeley users who have this article in their library.
  • 26

    Citations

    Citations of this article.

Abstract

Pure-silica zeolite beta containing Lewis acidic framework Ti4+ centers (Ti-Beta) is shown to catalyze the isomerization of D-glucose to L-sorbose via an intramolecular C5−C1 hydride shift. Glucose−sorbose isomerization occurs in parallel to glucose−fructose isomerization on Ti-Beta in both water and methanol solvents, with fructose formed as the predominant product in water and sorbose as the predominant product in methanol (at 373 K) at initial times and over the course of >10 turnovers. Isotopic tracer studies demonstrate that 13C and D labels placed respectively at the C1 and C2 positions of glucose are retained respectively at the C6 and C5 positions of sorbose, consistent with its formation via an intramolecular C5−C1 hydride shift isomerization mechanism. This direct Lewis acid-mediated pathway for glucose−sorbose isomerization appears to be unprecedented among heterogeneous or biological catalysts and sharply contrasts indirect basemediated glucose−sorbose isomerization via 3,4-enediol intermediates or via retro-aldol fragmentation and recombination of sugar fragments. Measured first-order glucose−sorbose isomerization rate constants (per total Ti; 373 K) for Ti-Beta in methanol are similar for glucose and glucose deuterated at the C2 position (within a factor of ∼1.1), but are a factor of ∼2.3 lower for glucose deuterated at each carbon position, leading to H/D kinetic isotope effects expected for kinetically relevant intramolecular C5−C1 hydride shift steps. Optical rotation measurements show that isomerization of D-(+)-glucose (92% enantiomeric purity) with Ti-Beta in water (373 K) led to the formation of L-(−)-sorbose (73% enantiomeric purity) and D-(−)-fructose (87% enantiomeric purity) as the predominant stereoisomers, indicating that stereochemistry is preserved at carbon centers not directly involved in intramolecular C5−C1 or C2−C1 hydride shift steps, respectively. This new Lewis acid-mediated rearrangement of glucose to sorbose does not appear to have a metalloenzyme analog.

Author-supplied keywords

  • Lewis acid
  • fructose
  • glucose
  • hydride shift
  • isomerization
  • sorbose
  • stereospecific
  • titanium-Beta

Get free article suggestions today

Mendeley saves you time finding and organizing research

Sign up here
Already have an account ?Sign in

Find this document

Get full text

Authors

  • Rajamani Gounder

  • Mark E. Davis

Cite this document

Choose a citation style from the tabs below

Save time finding and organizing research with Mendeley

Sign up for free