Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts

Chem Commun (Camb). 2021 Feb 23;57(15):1919-1922. doi: 10.1039/d0cc08142f.

Abstract

Here, the streptavidin-biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations.

MeSH terms

  • Biotin / chemistry*
  • Catalysis
  • Enzymes / chemistry
  • Enzymes / metabolism
  • Hydrogenation
  • Models, Molecular
  • Molecular Structure
  • Protein Conformation
  • Streptavidin / chemistry*

Substances

  • Enzymes
  • Biotin
  • Streptavidin