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A light-driven enzymatic enantioselective radical acylation.

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Summary

This study repurposes thiamine diphosphate (ThDP)-dependent enzymes for asymmetric radical transformations, creating chiral ketones from aldehydes with high selectivity using a novel dual biocatalysis and photocatalysis approach.

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Area of Science:

  • Biocatalysis
  • Organic Chemistry
  • Enzyme Engineering

Background:

  • Enzymes excel at stereoselective catalysis, but controlling radical reactions lags chemical methods.
  • Thiamine diphosphate (ThDP)-dependent enzymes inspired N-heterocyclic carbenes (NHCs) but haven't been used in asymmetric radical reactions.
  • Biocompatible radical generation is limited as biological systems often avoid reactive radicals.

Purpose of the Study:

  • To engineer a ThDP-dependent enzyme for stereoselective radical acyl transfer.
  • To develop a general and biocompatible asymmetric radical transformation method.
  • To combine biocatalysis with organophotoredox catalysis for radical control.

Main Methods:

  • Protein engineering of a ThDP-dependent lyase into a radical acyl transferase (RAT).
  • Utilizing organophotoredox catalysis to generate enzyme-bound ThDP-derived ketyl radicals.
  • Cross-coupling of ketyl radicals with prochiral alkyl radicals for asymmetric synthesis.

Main Results:

  • Successfully repurposed a ThDP-dependent enzyme as a stereoselective radical acyl transferase (RAT).
  • Achieved high enantioselectivity (up to 97% e.e.) in the synthesis of diverse chiral ketones from aldehydes.
  • Demonstrated a novel dual-enzyme catalysis/photocatalysis strategy for radical control.

Conclusions:

  • Expanded the scope of biocatalysis into asymmetric radical chemistry.
  • Provided a unique enzymatic strategy for controlling reactive radicals.
  • Developed a complementary tool to existing chemical methods for chiral synthesis.