Chemistry - A European Journal,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
Saturated
bioisosteres
of
ortho-substituted
benzenes
are
significant
interest
due
to
their
enhanced
pharmacokinetic
properties,
such
as
improved
metabolic
stability
and
reduced
toxicity,
making
them
valuable
in
drug
design
development.
However,
efficient
synthesis
remains
a
challenge
organic
chemistry.
Herein,
we
report
the
biocatalytic
saturated
using
engineered
artificial
photoenzymes.
The
photoenzyme,
incorporating
genetically
encoded
unnatural
amino
acids
with
benzophenone
photosensitizer
residue,
facilitate
formation
chiral
moderate
enantiomeric
excess
via
energy
transfer
process.
Our
results
demonstrate
versatility
photoenzymes
mediating
new-to-nature
reactions
that
difficult
achieve
conventional
chemical
or
enzymatic
methods.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(33), P. 23321 - 23329
Published: Aug. 6, 2024
Pyridoxal-5'-phosphate
(PLP)
and
derivatives
of
this
cofactor
enable
a
plethora
reactions
in
both
enzyme-mediated
free-in-solution
transformations.
With
few
exceptions
each
category,
such
chemistry
has
predominantly
involved
two-electron
processes.
This
sometimes
poses
significant
challenge
for
using
PLP
to
build
tetrasubstituted
carbon
centers,
especially
when
the
reaction
is
reversible.
The
ability
access
radical
pathways
paramount
broadening
scope
catalyzed
by
coenzyme.
In
study,
we
demonstrate
PLP-based
intermediate
engage
number
C-C
bond-forming
reactions.
By
selection
an
appropriate
oxidant,
single-electron
oxidation
quinonoid
can
be
achieved,
which
subsequently
applied
Through
pathway,
synthesized
series
α-tertiary
amino
acids
esters
investigate
substrate
identify
nonproductive
pathways.
Beyond
acid
model
system,
that
other
classes
amine
substrates
range
small
molecule
reagents
serve
as
coupling
partners
semiquinone
radical.
We
anticipate
versatile
species
will
central
development
novel
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2197 - 2201
Published: March 7, 2024
In
this
study,
we
present
an
N-heterocyclic
carbene-catalyzed
method
for
the
radical
acylphosphorylation
of
alkenes.
Electrochemical
investigations
were
employed
to
identify
appropriate
class
oxime
phosphonates
capable
undergoing
a
single-electron
transfer
(SET)
with
Breslow
enolates.
The
resulting
phosphoryl
radicals
effectively
coupled
diverse
styrenes
and
aldehydes
yield
variety
γ-oxo-phosphonates.
Both
clock
experiments
electrochemical
studies
support
our
reaction
design,
plausible
mechanism
organocatalytic
transformation
is
proposed.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Oct. 16, 2024
The
carboamination
of
unsaturated
molecules
using
bifunctional
reagents
is
considered
an
attractive
approach
for
the
synthesis
nitrogen-containing
compounds.
However,
C-N
have
never
been
employed
in
cyclopropane.
In
this
study,
we
use
N-heterocyclic
carbene
(NHC),
N-benzoyl
saccharin,
as
a
reagent
and
photoredox
catalyst
dual-catalyzed
1,3-aminoacylation
NHCs
play
multiple
roles,
functioning
Lewis
base
catalysts
to
activate
bonds,
promoting
oxidative
quenching
process
PC*,
acting
efficient
acyl
radical
transfer
formation
C-C
bonds.
between
excited-state
PC*
NHC
adduct
key
photooxidation
generality
aryl
cyclopropanes.
Chemistry - A European Journal,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
Saturated
bioisosteres
of
ortho-substituted
benzenes
are
significant
interest
due
to
their
enhanced
pharmacokinetic
properties,
such
as
improved
metabolic
stability
and
reduced
toxicity,
making
them
valuable
in
drug
design
development.
However,
efficient
synthesis
remains
a
challenge
organic
chemistry.
Herein,
we
report
the
biocatalytic
saturated
using
engineered
artificial
photoenzymes.
The
photoenzyme,
incorporating
genetically
encoded
unnatural
amino
acids
with
benzophenone
photosensitizer
residue,
facilitate
formation
chiral
moderate
enantiomeric
excess
via
energy
transfer
process.
Our
results
demonstrate
versatility
photoenzymes
mediating
new-to-nature
reactions
that
difficult
achieve
conventional
chemical
or
enzymatic
methods.
