ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9144 - 9150
Published: May 30, 2024
Despite
substantial
progress
made
toward
elucidating
the
natural
radical
enzymology
with
thiamine
pyrophosphate
(TPP)-dependent
pyruvate:ferredoxin
oxidoreductases
(PFORs)
and
pyruvate
oxidases
(POXs),
repurposing
naturally
occurring
two-electron
TPP-dependent
enzymes
to
catalyze
single-electron
transformations
significant
synthetic
value
remains
a
daunting
task.
Enabled
by
synergistic
use
of
visible-light
photocatalyst
fluorescein
set
engineered
derived
from
benzoylformate
decarboxylase
(BFD)
benzaldehyde
lyase
(BAL),
we
developed
an
asymmetric
photobiocatalytic
decarboxylative
alkylation
benzaldehydes
α-keto
acids
produce
highly
enantioenriched
α-branched
ketones.
Mechanistically,
propose
that
this
dual
catalytic
involves
oxidation
enzyme-bound
Breslow
intermediate
subsequent
interception
photoredox-generated
transient
alkyl
radical.
In
conjunction
visible
light
photoredox
catalysis,
biocatalysis
represents
emerging
platform
discover
optimize
are
unknown
biological
systems
not
amenable
small-molecule
catalysis.
Science,
Journal Year:
2023,
Volume and Issue:
382(6673)
Published: Nov. 23, 2023
Biocatalysis
harnesses
enzymes
to
make
valuable
products.
This
green
technology
is
used
in
countless
applications
from
bench
scale
industrial
production
and
allows
practitioners
access
complex
organic
molecules,
often
with
fewer
synthetic
steps
reduced
waste.
The
last
decade
has
seen
an
explosion
the
development
of
experimental
computational
tools
tailor
enzymatic
properties,
equipping
enzyme
engineers
ability
create
biocatalysts
that
perform
reactions
not
present
nature.
By
using
(chemo)-enzymatic
synthesis
routes
or
orchestrating
intricate
cascades,
scientists
can
synthesize
elaborate
targets
ranging
DNA
pharmaceuticals
starch
made
vitro
CO2-derived
methanol.
In
addition,
new
chemistries
have
emerged
through
combination
biocatalysis
transition
metal
catalysis,
photocatalysis,
electrocatalysis.
review
highlights
recent
key
developments,
identifies
current
limitations,
provides
a
future
prospect
for
this
rapidly
developing
technology.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2748 - 2756
Published: Jan. 12, 2024
Controlling
the
enantioselectivity
of
hydrogen
atom
transfer
(HAT)
reactions
has
been
a
long-standing
synthetic
challenge.
While
recent
advances
on
photoenzymatic
catalysis
have
demonstrated
great
potential
non-natural
photoenzymes,
all
transformations
are
initiated
by
single-electron
reduction
substrate,
with
only
one
notable
exception.
Herein,
we
report
an
oxidation-initiated
enantioselective
hydrosulfonylation
olefins
using
novel
mutant
gluconobacter
ene-reductase
(GluER-W100F-W342F).
Compared
to
known
systems,
our
approach
does
not
rely
formation
electron
donor–acceptor
complex
between
substrates
and
enzyme
cofactor
simplifies
reaction
system
obviating
addition
regeneration
mixture.
More
importantly,
GluER
variant
exhibits
high
reactivity
broad
substrate
scope.
Mechanistic
studies
support
proposed
mechanism
reveal
that
tyrosine-mediated
HAT
process
is
involved.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1209 - 1223
Published: Jan. 3, 2024
Owing
to
its
diverse
activation
processes
including
single-electron
transfer
(SET)
and
hydrogen-atom
(HAT),
visible-light
photocatalysis
has
emerged
as
a
sustainable
efficient
platform
for
organic
synthesis.
These
provide
powerful
avenue
the
direct
functionalization
of
C(sp3)–H
bonds
under
mild
conditions.
Over
past
decade,
there
have
been
remarkable
advances
in
enantioselective
bond
via
combined
with
conventional
asymmetric
catalysis.
Herein,
we
summarize
involving
discuss
two
main
pathways
this
emerging
field:
(a)
SET-driven
carbocation
intermediates
are
followed
by
stereospecific
nucleophile
attacks;
(b)
photodriven
alkyl
radical
further
enantioselectively
captured
(i)
chiral
π-SOMOphile
reagents,
(ii)
stereoselective
transition-metal
complexes,
(iii)
another
distinct
stereoscopic
species.
We
aim
key
reaction
design,
catalyst
development,
mechanistic
understanding,
new
insights
into
rapidly
evolving
area
research.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(9), P. 1446 - 1457
Published: April 11, 2024
ConspectusEnzymes
are
desired
catalysts
for
chemical
synthesis,
because
they
can
be
engineered
to
provide
unparalleled
levels
of
efficiency
and
selectivity.
Yet,
despite
the
astonishing
array
reactions
catalyzed
by
natural
enzymes,
many
reactivity
patterns
found
in
small
molecule
have
no
counterpart
living
world.
With
a
detailed
understanding
mechanisms
utilized
catalysts,
we
identify
existing
enzymes
with
potential
catalyze
that
currently
unknown
nature.
Over
past
eight
years,
our
group
has
demonstrated
flavin-dependent
"ene"-reductases
(EREDs)
various
radical-mediated
selectivity,
solving
long-standing
challenges
asymmetric
synthesis.This
Account
presents
development
EREDs
as
general
radical
reactions.
While
developed
multiple
generating
radicals
within
protein
active
sites,
this
account
will
focus
on
examples
where
flavin
mononucleotide
hydroquinone
(FMNhq)
serves
an
electron
transfer
initiator.
initial
mechanistic
hypotheses
were
rooted
electron-transfer-based
initiation
commonly
used
synthetic
organic
chemists,
ultimately
uncovered
emergent
unique
site.
We
begin
covering
intramolecular
discussing
how
activates
substrate
reduction
altering
redox-potential
alkyl
halides
templating
charge
complex
between
flavin-cofactor.
Protein
engineering
been
modify
fundamental
photophysics
these
reactions,
highlighting
opportunity
tune
systems
further
using
directed
evolution.
This
section
highlights
range
coupling
partners
termination
available
reactions.The
next
intermolecular
role
enzyme-templated
ternary
complexes
among
cofactor,
halide,
partner
gating
ensure
it
only
occurs
when
both
substrates
bound
highlight
applications
activation
mode,
including
olefin
hydroalkylation,
carbohydroxylation,
arene
functionalization,
nitronate
alkylation.
also
discusses
favor
steps
elusive
solution
reductive
nitroalkanes.
aware
several
recent
EREDs-catalyzed
photoenzymatic
transformations
from
other
groups.
discuss
results
papers
context
nuances
substrates.These
biocatalytic
often
complement
state-of-the-art
small-molecule-catalyzed
making
valuable
addition
chemist's
toolbox.
Moreover,
underlying
principles
studied
potentially
operative
cofactor-dependent
proteins,
opening
door
different
types
enzyme-catalyzed
anticipate
serve
guide
inspire
broad
interest
repurposing
access
new
transformations.
JACS Au,
Journal Year:
2024,
Volume and Issue:
4(8), P. 2746 - 2766
Published: Aug. 8, 2024
Photocatalysis
is
a
versatile
and
rapidly
developing
field
with
applications
spanning
artificial
photosynthesis,
photo-biocatalysis,
photoredox
catalysis
in
solution
or
supramolecular
structures,
utilization
of
abundant
metals
organocatalysts,
sustainable
synthesis,
plastic
degradation.
In
this
Perspective,
we
summarize
conclusions
from
an
interdisciplinary
workshop
young
principal
investigators
held
at
the
Lorentz
Center
Leiden
March
2023.
We
explore
how
diverse
fields
within
photocatalysis
can
benefit
one
another.
delve
into
intricate
interplay
between
these
subdisciplines,
by
highlighting
unique
challenges
opportunities
presented
each
multidisciplinary
approach
drive
innovation
lead
to
solutions
for
future.
Advanced
collaboration
knowledge
exchange
across
domains
further
enhance
potential
photocatalysis.
Artificial
photosynthesis
has
become
promising
technology
solar
fuel
generation,
instance,
via
water
splitting
CO
Russian Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
92(12), P. RCR5104 - RCR5104
Published: Dec. 1, 2023
After
the
appearance
of
green
chemistry
concept,
which
was
introduced
in
vocabulary
early
1990s,
its
main
statements
have
been
continuously
developed
and
modified.
Currently,
there
are
10–12
cornerstones
that
should
form
basis
for
an
ideal
chemical
process.
This
review
analyzes
accumulated
experience
achievements
towards
design
products
processes
reduce
or
eliminate
use
generation
hazardous
substances.
The
presents
views
leading
Russian
scientists
specializing
various
fields
this
subject,
including
homogeneous
heterogeneous
catalysis,
fine
basic
organic
synthesis,
electrochemistry,
polymer
chemistry,
based
on
bio-renewable
feedstocks
energetic
compounds
materials.
A
new
approach
to
quantitative
evaluation
environmental
friendliness
by
authors
is
described.
<br>
bibliography
includes
1761.