The role and mechanisms of canonical and non-canonical tailoring enzymes in bacterial terpenoid biosynthesis
Natural Product Reports,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
explores
recent
insights
into
the
roles
and
enzymatic
mechanisms
of
canonical
non-canonical
tailoring
enzymes
in
shaping
modifying
terpene
hydrocarbon
scaffolds
during
bacterial
biosynthesis.
Язык: Английский
Characterization of an α‐ketoglutarate‐dependent oxygenase involved in converting 2‐(2‐phenylethyl)chromones into 2‐styrylchromones in agarwood
The Plant Journal,
Год журнала:
2025,
Номер
121(5)
Опубликована: Март 1, 2025
2-Phenylethylchromones
(PECs)
and
2-styrylchromones
(SCs)
are
the
primary
components
responsible
for
delightful
fragrance
bioactivity
of
agarwood,
a
highly
valuable
aromatic
resinous
heartwood.
PECs
derived
from
common
precursor
with
diarylpentanoid
skeleton
(C6-C5-C6).
However,
biosynthesis
SCs
remains
unclear.
In
this
study,
based
on
successful
conversion
PEC
skeleton,
rather
than
dehydrogenated
diarylpentanoid,
into
by
Aquilaria
sinensis
suspension
cells,
we
demonstrated
that
double
bond
formation
styryl
group
in
occurs
after
creation
not
before
step
precursor.
Through
transcriptomic
data
mining,
transient
expression
Nicotiana
benthamiana
A.
identified
new
2-oxoglutarate-dependent
oxygenase
(As2OG1)
plays
crucial
role
SCs.
Further
protein
structure
prediction
mutagenesis
studies,
combined
probing
catalytic
potential
As2OG1
using
chemically
synthesized
hydroxylated
intermediates,
suggested
possibly
uses
diradical
or
carbocation
to
install
bonds
The
results
only
provide
insights
molecular
mechanism
agarwood
but
also
facilitate
overproduction
pharmaceutically
important
metabolic
engineering
approaches.
Язык: Английский
Concise Biosynthesis of Antifungal Papulacandins
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 5, 2025
We
report
the
complete
biosynthesis
of
antifungal
papulacandins
through
heterologous
expression
and
enzymatic
assays.
The
papulacandin
follows
a
convergent
five-component
strategy,
involving
linear
polyketide
chain
that
is
synthesized
installed
to
aryl-glucoside
by
synthase
fused
with
C-terminal
acyltransferase
domain.
formation
challenging
tricyclic
benzannulated
spiroketal
core
initiated
C-glycosylation
5-(hydroxymethyl)resorcinol,
followed
spirocyclization
catalyzed
Fe(II)/α-ketoglutarate-dependent
oxygenase
PpcE.
Язык: Английский
Cytochrome P450-Catalyzed Allylic Oxidation of Pentalenene to 1-Deoxypentalenic Acid in Pentalenolactone Biosynthesis
Engineering Microbiology,
Год журнала:
2025,
Номер
unknown, С. 100206 - 100206
Опубликована: Апрель 1, 2025
Язык: Английский
An Alternative Mechanism for C–C Desaturation Underscores a Dual-Controlled Mechanism for the Fate of Radical Intermediate in Iron(II)- and 2-(Oxo)glutarate-Dependent Oxygenase DfmD
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Июнь 6, 2025
The
C(sp3)-C(sp3)
desaturation
catalyzed
by
iron(II)-
and
2-(oxo)glutarate-dependent(Fe/2OG)
oxygenase
is
a
key
step
in
the
biosynthesis
modification
of
natural
products.
Similar
to
other
C-H
functionalization
processes,
reaction
initiated
active
Fe(IV)-oxo
species,
which
abstracts
hydrogen
atom
from
bond.
However,
Fe/2OG
desaturase
suppresses
thermodynamically
favored
OH-rebound
process.
This
enigmatic
since
substrate-cofactor
disposition
appears
be
favorable
process
involves
activation
followed
OH
rebound.
To
decipher
mechanism,
we
studied
here
dehydrofosmidomycin
DfmD,
an
enzyme
that
catalyzes
product
through
desaturation,
rearrangement,
demethylation
reactions.
study
employed
biochemical,
crystallographic,
computational
analysis
reaction.
Unlike
sequential
hydrogen-atom
transfer
(HAT)
mechanism
cation-dependent
our
reveals
alternative
for
C-C
desaturation.
formation
three-member
ring
intermediate
oxaphosphiran.
We
found
oxaphosphiran
reduced
barrier
Additionally,
H-bonding
network
disfavors
pathway.
As
such,
this
dual
action
enables
selective
while
bypassing
hydroxylation
highlights
importance
protein
machinery
as
means
controlling
reactivity
selectivity
radical
species.
Язык: Английский