The Royal Society of Chemistry eBooks,
Journal Year:
2020,
Volume and Issue:
unknown, P. 131 - 180
Published: July 14, 2020
Oxidoreductase
enzymes
enable
a
large
variety
of
oxidation
and
oxyfunctionalization
reactions
at
the
expense
molecular
oxygen,
which
is
most
commonly
used
in
form
air
atmospheric
pressure.
Over
past
decade,
number
available
methodologies
enabling
performance
these
types
has
increased
significantly,
thereby
greatly
complicating
navigation
biochemical
landscape
aerobic
enzymatic
reactions.
This
chapter
provides
an
overview
bio-catalytic
that
utilize
dioxygen
as
final
electron
acceptor
or
hydroxylating
agent
with
focus
on
more
mature
processes
allow
least
gram-scale
biotransformations
significant
chemical
turnovers,
thus
demonstrating
practical
applicability
organic
synthesis.
The
described
comprise:
(a)
carbon–hydrogen
hydroxylation
halogenation;
(b)
mono-
di-hydroxylation
well
epoxidation
cleavage
alkenes;
(c)
Baeyer–Villiger
oxidation;
(d)
alcohols
aldehydes;
oxidative
decarboxylation;
(e)
amines
imines;
organosulfur,
organoboron
organoselenium
compounds;
(f)
carbon–carbon
bond
formation.
Additionally,
this
brief
selected
mechanistic
insights
into
enzyme
classes
(i.e.,
oxygenases,
oxidases,
dehydrogenases)
catalyze
transformations
often
excellent
chemo-,
regio-
stereoselectivities.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(31), P. 16824 - 16855
Published: Jan. 16, 2021
Enzyme
catalysis
is
gaining
increasing
importance
in
synthetic
chemistry.
Nowadays,
the
growing
number
of
biocatalysts
accessible
by
means
bioinformatics
and
enzyme
engineering
opens
up
an
immense
variety
selective
reactions.
Biocatalysis
especially
provides
excellent
opportunities
for
late-stage
modification
often
superior
to
conventional
de
novo
synthesis.
Enzymes
have
proven
be
useful
direct
introduction
functional
groups
into
complex
scaffolds,
as
well
rapid
diversification
compound
libraries.
Particularly
important
highly
topical
are
enzyme-catalysed
oxyfunctionalisations,
halogenations,
methylations,
reductions,
amide
bond
formations
due
high
prevalence
these
motifs
pharmaceuticals.
This
Review
gives
overview
strengths
limitations
enzymatic
modifications
using
native
engineered
enzymes
synthesis
while
focusing
on
examples
drug
development.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Nov. 21, 2022
The
process
of
recycling
poly(ethylene
terephthalate)
(PET)
remains
a
major
challenge
due
to
the
enzymatic
degradation
high-crystallinity
PET
(hcPET).
Recently,
bacterial
PET-degrading
enzyme,
PETase,
was
found
have
ability
degrade
hcPET,
but
with
low
activity.
Here
we
present
an
engineered
whole-cell
biocatalyst
simulate
both
adsorption
and
steps
in
PETase
achieve
efficient
hcPET.
Our
data
shows
that
adhesive
unit
hydrophobin
are
functionally
displayed
on
surface
yeast
cells.
turnover
rate
toward
hcPET
(crystallinity
45%)
dramatically
increases
approximately
328.8-fold
compared
purified
at
30
°C.
In
addition,
molecular
dynamics
simulations
explain
how
enhanced
adhesion
can
promote
PET.
This
study
demonstrates
engineering
catalyst
is
strategy
for
biodegradation
ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
8(12), P. 11889 - 11907
Published: Nov. 8, 2018
Monoamine
oxidases
(MAO)
are
biocatalysts
for
the
oxidation
of
a
wide
range
different
amines
including
α-chiral
amines.
Their
high
selectivity
and
activity,
along
with
environmental
advantages
inherent
to
enzymatic
synthesis,
place
MAOs
in
spotlight
future
application
industrial
biocatalytic
processes.
To
date,
these
enzymes
have
been
used
both
amine
resolution
functionalization.
MAO
from
Micrococcus
luteus
was
employed
multienzymatic
synthesis
benzylisoquinoline
alkaloids,
Aspergillus
niger
(MAO-N)
deracemization
experiments.
MAO-N
also
applied
several
biobio
biochemo
cascades
functionalization,
exploring
increased
reactivity
imine/iminium
species.
has
extensively
engineered
alter
size
electronic
properties
its
active
site,
creating
variants
capable
oxidizing
broad
α-aliphatic
aromatic
This
Review
provides
an
in-depth
analysis
current
research
applications
MAOs,
coupled
available
data
on
limitations
challenges
that
still
hinder
their
application.
It
highlights
importance
chiral
biochemical
human
metabolism.
Finally,
development
alternative
oxidases,
such
as
CHAO
or
HLNO/HDNO,
is
briefly
surveyed,
discussion
possible
developments
this
field.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21088 - 21095
Published: Nov. 9, 2022
The
development
of
efficient
and
sustainable
methods
for
the
synthesis
nitrogen
heterocycles
is
an
important
goal
chemical
industry.
In
particular,
substituted
chiral
piperidines
are
prominent
targets
due
to
their
prevalence
in
medicinally
relevant
compounds
precursors.
A
potential
biocatalytic
approach
this
privileged
scaffold
would
be
asymmetric
dearomatization
readily
assembled
activated
pyridines.
However,
nature
yet
yield
a
suitable
biocatalyst
specifically
reaction.
Here,
by
combining
biocatalysis,
we
present
general
chemo-enzymatic
pyridines
preparation
with
precise
stereochemistry.
key
step
involves
stereoselective
one-pot
amine
oxidase/ene
imine
reductase
cascade
convert
N-substituted
tetrahydropyridines
stereo-defined
3-
3,4-substituted
piperidines.
This
has
proved
useful
transformations
syntheses
antipsychotic
drugs
Preclamol
OSU-6162,
as
well
two
intermediates
synthetic
routes
ovarian
cancer
monotherapeutic
Niraparib.
Flavour and Fragrance Journal,
Journal Year:
2023,
Volume and Issue:
38(4), P. 221 - 242
Published: April 10, 2023
Many
aldehydes
are
volatile
compounds
with
distinct
and
characteristic
olfactory
properties.
The
aldehydic
functional
group
is
reactive
and,
as
such,
an
invaluable
chemical
multi-tool
to
make
all
sorts
of
products.
Owing
the
reactivity,
selective
synthesis
a
challenging
task.
Nature
has
evolved
number
enzymatic
reactions
produce
aldehydes,
this
review
provides
overview
aldehyde-forming
in
biological
systems
beyond.
Whereas
some
these
biotransformations
still
their
infancy
terms
synthetic
applicability,
others
developed
extent
that
allows
implementation
industrial
biocatalysts.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(8), P. 4431 - 4437
Published: Feb. 15, 2023
Herein,
we
report
a
one-pot,
chemoenzymatic
process
for
the
synthesis
of
enantioenriched
C(1)-allylated
tetrahydroisoquinolines.
This
transformation
couples
monoamine
oxidase
(MAO-N)-catalyzed
oxidation
with
metal
catalyzed
allylboration,
followed
by
biocatalytic
deracemization
to
afford
allylic
amine
derivatives
in
both
high
yields
and
good
enantiomeric
excess.
The
cascade
is
operationally
simple,
all
components
added
at
start
reaction
can
be
used
generate
key
building
blocks
further
elaboration.
