Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(2), С. 787 - 793
Опубликована: Янв. 6, 2023
Tertiary
nitroalkanes
and
the
corresponding
α-tertiary
amines
represent
important
motifs
in
bioactive
molecules
natural
products.
The
C-alkylation
of
secondary
with
electrophiles
is
a
straightforward
strategy
for
constructing
tertiary
nitroalkanes;
however,
controlling
stereoselectivity
this
type
reaction
remains
challenging.
Here,
we
report
highly
chemo-
stereoselective
alkyl
halides
catalyzed
by
an
engineered
flavin-dependent
"ene"-reductase
(ERED).
Directed
evolution
old
yellow
enzyme
from
Geobacillus
kaustophilus
provided
triple
mutant,
GkOYE-G7,
capable
synthesizing
high
yield
enantioselectivity.
Mechanistic
studies
indicate
that
excitation
enzyme-templated
charge-transfer
complex
formed
between
substrates
cofactor
responsible
radical
initiation.
Moreover,
single-enzyme
two-mechanism
cascade
was
developed
to
prepare
simple
nitroalkenes,
highlighting
potential
use
one
two
mechanistically
distinct
reactions.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(7), С. 2759 - 2852
Опубликована: Янв. 1, 2022
C-H
functionalization
has
been
emerging
as
a
powerful
method
to
establish
carbon-carbon
and
carbon-heteroatom
bonds.
Many
efforts
have
devoted
transition-metal-catalyzed
direct
transformations
of
Metal
carbenes
generated
in
situ
from
transition-metal
compounds
diazo
or
its
equivalents
are
usually
applied
the
transient
reactive
intermediates
furnish
catalytic
cycle
for
new
C-C
C-X
bond
formation.
Using
this
strategy
unactivated
simple
alkanes
complex
molecules
can
be
further
functionalized
transformed
multi-functionalized
compounds.
In
area,
carbene
insertion
bonds
paid
continuous
attention.
Diverse
catalyst
design
strategies,
synthetic
methods,
potential
applications
developed.
This
critical
review
will
summarize
advance
dated
up
July
2021,
by
categories
aliphatic
C(sp3)-H,
aryl
(aromatic)
C(sp2)-H,
heteroaryl
(heteroaromatic)
C(sp2)-H
bonds,
alkenyl
alkynyl
C(sp)-H,
well
asymmetric
more
coverage
given
recent
work.
Due
rapid
development
future
directions
topic
also
discussed.
give
authors
an
overview
chemistry
with
focus
on
systems
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.
Green Chemistry,
Год журнала:
2023,
Номер
25(5), С. 1704 - 1728
Опубликована: Янв. 1, 2023
Publication
of
the
E
Factor
drew
attention
to
problem
waste
in
chemicals
manufacture.
Thirty
yeas
later
it
is
abundantly
clear
that
underlying
cause
global
environmental
problems,
from
climate
change
plastic
pollution.
Science,
Год журнала:
2021,
Номер
374(6575), С. 1612 - 1616
Опубликована: Дек. 23, 2021
Naturally
occurring
enzymes
can
be
a
source
of
unnatural
reactivity
that
molded
by
directed
evolution
to
generate
efficient
biocatalysts
with
valuable
activities.
Owing
the
lack
exploitable
stereocontrol
elements
in
synthetic
systems,
steering
absolute
and
relative
stereochemistry
free-radical
processes
is
notoriously
difficult
asymmetric
catalysis.
Inspired
innate
redox
properties
first-row
transition-metal
cofactors,
we
repurposed
cytochromes
P450
catalyze
stereoselective
atom-transfer
radical
cyclization.
A
set
metalloenzymes
was
engineered
impose
substantial
over
addition
step
halogen
rebound
these
processes,
allowing
enantio-
diastereodivergent
This
evolvable
metalloenzyme
platform
represents
promising
solution
tame
fleeting
intermediates
for
Chemical Reviews,
Год журнала:
2022,
Номер
122(14), С. 11974 - 12045
Опубликована: Июль 11, 2022
Metalloenzymes
catalyze
a
variety
of
reactions
using
limited
number
natural
amino
acids
and
metallocofactors.
Therefore,
the
environment
beyond
primary
coordination
sphere
must
play
an
important
role
in
both
conferring
tuning
their
phenomenal
catalytic
properties,
enabling
active
sites
with
otherwise
similar
environments
to
perform
diverse
array
biological
functions.
However,
since
interactions
are
numerous
weak,
it
has
been
difficult
pinpoint
structural
features
responsible
for
activities
native
enzymes.
Designing
artificial
metalloenzymes
(ArMs)
offers
excellent
basis
elucidate
roles
these
further
develop
practical
catalysts.
In
this
review,
we
highlight
how
secondary
spheres
ArMs
influence
metal
binding
catalysis,
particular
focus
on
use
protein
scaffolds
as
templates
design
by
either
rational
aided
computational
modeling,
directed
evolution,
or
combination
approaches.
describing
successes
designing
heme,
nonheme
Fe,
Cu
metalloenzymes,
heteronuclear
containing
those
other
centers
(including
non-native
ions
metallocofactors),
have
summarized
insights
gained
careful
controls
sphere,
including
hydrophobic
hydrogen
bonding
interactions,
allow
generation
respective
systems
approach,
rival,
and,
few
cases,
exceed
We
also
provided
outlook
remaining
challenges
field
future
directions
that
will
deeper
understanding
coordintion
be
gained,
turn
guide
broader
more
efficient
ArMs.
Science,
Год журнала:
2023,
Номер
381(6656), С. 444 - 451
Опубликована: Июль 27, 2023
Developing
synthetically
useful
enzymatic
reactions
that
are
not
known
in
biochemistry
and
organic
chemistry
is
an
important
challenge
biocatalysis.
Through
the
synergistic
merger
of
photoredox
catalysis
pyridoxal
5'-phosphate
(PLP)
biocatalysis,
we
developed
a
radical
biocatalysis
approach
to
prepare
valuable
noncanonical
amino
acids,
including
those
bearing
stereochemical
dyad
or
triad,
without
need
for
protecting
groups.
Using
engineered
PLP
enzymes,
either
enantiomeric
product
could
be
produced
biocatalyst-controlled
fashion.
Synergistic
