Allylations are practical transformations that forge
C–C
bonds while introducing an alkene for further chemical manipulations.
Here, we report a photoenzymatic allylation of α-chloroamides with allyl silanes using flavin-dependent “ene”-reductases
(EREDs). An engineered ERED can catalyze annulative allylic alkylation
to prepare 5, 6, and 7-membered lactams with high levels of enantioselectivity.
Ultrafast transient absorption spectroscopy indicates that radical
termination occurs via β-scission of the silyl group to afford
a silyl radical, a distinct mechanism by comparison to traditional
radical allylations involving allyl silanes. Moreover, this represents
an alternative strategy for radical termination using EREDs. This
mechanism was applied to intermolecular couplings involving allyl
sulfones and silyl enol ethers. Overall, this method highlights the
opportunity for EREDs to catalyze radical termination strategies beyond
hydrogen atom transfer.
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