Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(38), С. 25976 - 25985
Опубликована: Авг. 8, 2024
Cerium
photoredox
catalysis
has
emerged
as
a
powerful
strategy
to
activate
molecules
under
mild
conditions.
Radical
intermediates
are
formed
using
visible
light
and
simple
complexes
of
the
earth-abundant
lanthanide.
Here,
we
report
an
artificial
photoenzyme
enabling
this
chemistry
inside
protein.
We
utilize
de
novo
designed
protein
scaffold
that
tightly
binds
lanthanide
ions
in
its
central
cavity.
Upon
visible-light
irradiation,
cerium-dependent
enzyme
catalyzes
radical
C-C
bond
cleavage
1,2-diols
aqueous
solution.
Protein
engineering
led
variants
with
improved
photostability
metal
binding
behavior.
The
cleaves
range
aromatic
aliphatic
substrates,
including
lignin
surrogates.
Surface
display
on
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6710 - 6716
Опубликована: Апрель 16, 2024
The
photoinduced
unnatural
reactions
catalyzed
by
flavin-dependent
enzymes
usually
proceed
through
reduction
pathways,
which
required
the
use
of
electron-sacrificial
reagents.
Herein,
we
developed
a
photoenzymatic
redox-neutral
radical
hydrosulfonylation
induced
oxidated
flavin
(FMN)
with
sulfinates
or
sulfonyl
hydrazines
as
precursors.
reaction
involved
excited
FMN
acquiring
an
electron
from
substrate,
and
resulting
sulfuryl
was
captured
alkene.
It
is
then
stereoselectively
quenched
semiquinone
(FMNsq)
hydrogen
atom
transfer.
This
study
circumvents
need
for
NADPH
recycling
systems
expands
potential
patterns
in
photobiocatalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(18), С. 12691 - 12701
Опубликована: Апрель 27, 2024
Aliphatic
strained
rings
have
been
increasingly
applied
in
medicinal
chemistry
due
to
their
beneficial
physicochemical
and
pharmacokinetic
properties.
However,
the
divergent
synthesis
of
enantioenriched
cyclobutane
derivatives
with
various
structural
patterns
continues
be
a
significant
challenge.
Here,
we
disclose
palladium-catalyzed
enantioselective
desymmetrization
cyclobutenes,
resulting
series
hydroarylation
1,2-
1,3-diarylation
products
via
interceptions
common
Heck
intermediate.
Mechanistic
investigations
provide
valuable
insights
into
understanding
catalytic
mode
palladium
catalysts
observed
variations
deuterium-responsive
behavior
during
reactions.
Furthermore,
synthetic
utility
is
demonstrated
syntheses
deuterated
drug
candidate
belaperidone
skeletons
pseudosymmetrical
truxinic
acid-type
derivatives.
JACS Au,
Год журнала:
2024,
Номер
4(6), С. 2068 - 2080
Опубликована: Май 31, 2024
Biocatalysis
is
currently
undergoing
a
profound
transformation.
The
field
moves
from
relying
on
nature's
chemical
logic
to
discipline
that
exploits
generic
activation
modes,
allowing
for
novel
biocatalytic
reactions
and,
in
many
instances,
entirely
new
chemistry.
Generic
modes
enable
wide
range
of
reaction
types
and
played
pivotal
role
advancing
the
fields
organo-
photocatalysis.
This
perspective
aims
summarize
principal
harnessed
enzymes
develop
biocatalysts.
Although
extensively
researched
past,
highlighted
when
applied
within
enzyme
active
sites,
facilitate
transformations
have
largely
eluded
efficient
selective
catalysis.
advance
attributed
multiple
tunable
interactions
substrate
binding
pocket
precisely
control
competing
pathways
transition
states.
We
will
highlight
cases
synthetic
methodologies
achieved
by
engineered
provide
insights
into
potential
future
developments
this
rapidly
evolving
field.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 17054 - 17065
Опубликована: Июнь 13, 2024
Developing
new
methods
to
engineer
photobiocatalytic
reactions
is
of
utmost
significance
for
artificial
photosynthesis,
but
it
remains
a
grand
challenge
due
the
intrinsic
incompatibility
biocatalysts
with
photocatalysts.
In
this
work,
photocatalysts
and
enzymes
were
spatially
colocalized
at
Pickering
droplet
interfaces,
where
reaction
microenvironment
spatial
distance
between
two
distinct
catalysts
exquisitely
regulated
achieve
unprecedented
cascade
reactions.
As
proof
concept,
ultrathin
graphitic
carbon
nitride
nanosheets
loaded
Au
nanoparticles
precisely
positioned
in
outer
interfacial
layer
oil
droplets
produce
H2O2
under
light
irradiation,
while
exactly
placed
inner
catalyze
subsequent
biocatalytic
oxidation
using
situ
formed
as
an
oxidant.
alkene
epoxidation
thioether
oxidation,
our
cascades
showed
2.0–5.8-fold
higher
overall
efficiency
than
bulk
water
phase.
It
was
demonstrated
that
localization
photocatalyst
enzyme
interfaces
not
only
provided
their
respective
preferable
environments
intimate
proximity
rapid
transport
also
protected
from
oxidative
inactivation
caused
by
photogenerated
species.
These
remarkable
effects
contributed
significantly
enhanced
cascading
efficiency.
Our
work
presents
innovative
system
manifold
benefits,
providing
cutting-edge
platform
solar-driven
chemical
transformations
via
photobiocatalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(38), С. 25976 - 25985
Опубликована: Авг. 8, 2024
Cerium
photoredox
catalysis
has
emerged
as
a
powerful
strategy
to
activate
molecules
under
mild
conditions.
Radical
intermediates
are
formed
using
visible
light
and
simple
complexes
of
the
earth-abundant
lanthanide.
Here,
we
report
an
artificial
photoenzyme
enabling
this
chemistry
inside
protein.
We
utilize
de
novo
designed
protein
scaffold
that
tightly
binds
lanthanide
ions
in
its
central
cavity.
Upon
visible-light
irradiation,
cerium-dependent
enzyme
catalyzes
radical
C-C
bond
cleavage
1,2-diols
aqueous
solution.
Protein
engineering
led
variants
with
improved
photostability
metal
binding
behavior.
The
cleaves
range
aromatic
aliphatic
substrates,
including
lignin
surrogates.
Surface
display
on
