Abstract
We recently achieved an oxidation-initiated photoenzymatic enantioselective hydrosulfonylation
of olefins through the utilization of a new Gluconobacter ene-reductase mutant (GluER-W100F-W342F).
Our method simplifies the reaction system by eliminating the need for a cofactor regeneration
mixture and, in contrast with previous photoenzymatic systems, does not depend on
the formation of an electron donor–acceptor (EDA) complex between the substrates and
enzyme cofactor. Moreover, the GluER variant exhibits good substrate compatibility
and excellent enantioselectivity. Mechanistic investigations indicate that a tyrosine-mediated
HAT process is involved and support the proposed oxidation-initiated mechanism. In
this Synpacts article, we discuss the conceptual framework that led to the discovery
of this reaction and reflect on the key aspects of its development.
1 Introduction
2 Conceptual Background
2.1 Intramolecular Photoenzymatic Reactions via Single-Electron Reduction
2.2 Intermolecular Photoenzymatic Reactions via Single-Electron Reduction
3 The Development of the Process
4 Conclusion
Key words
photoenzymatic catalysis - hydrogen atom transfer - hydrosulfonylation - single-electron
oxidation - directed evolution
