Alkene Synthesis by Photocatalytic Chemoenzymatically Compatible Dehydrodecarboxylation of Carboxylic Acids and Biomass

Direct conversion
of renewable biomass and bioderived chemicals
to valuable synthetic intermediates for organic synthesis and materials
science applications by means of mild and chemoselective catalytic
methods has largely remained elusive. Development of artificial catalytic
systems that are compatible with enzymatic reactions provides a synergistic
solution to this enduring challenge by leveraging previously unachievable
reactivity and selectivity modes. We report herein a dual catalytic
dehydrodecarboxylation reaction that is enabled by a crossover of
the photoinduced acridine-catalyzed O–H hydrogen atom transfer
(HAT) and cobaloxime-catalyzed C–H-HAT processes. The reaction
produces a variety of alkenes from readily available carboxylic acids.
The reaction can be embedded in a scalable triple-catalytic cooperative
chemoenzymatic lipase–acridine–cobaloxime process that
allows for direct conversion of plant oils and biomass to long-chain
terminal alkenes, precursors to bioderived polymers.