Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: April 15, 2020
Abstract
Hetero-Diels-Alder
(HDA)
reaction
is
an
important
synthetic
method
for
many
natural
products.
An
iron(III)
catalyst
was
developed
to
catalyze
the
challenging
HDA
of
unactivated
aldehydes
and
dienes
with
high
selectivity.
Here
we
report
extensive
density-functional
theory
(DFT)
calculations
molecular
dynamics
simulations
that
show
effects
iron
(including
its
coordinate
mode
and/or
spin
state)
on
this
reaction:
considerably
enhancing
dynamically
stepwise
process,
broadening
entrance
channel
narrowing
exit
from
concerted
asynchronous
transition
states.
Also,
our
combined
computational
experimental
secondary
KIE
studies
reveal
unexpectedly
large
values
five-coordinate
pathway
even
considerable
C–C
bond
forming,
due
equilibrium
isotope
effect
change
in
metal
coordination.
Moreover,
steric
electronic
are
computationally
shown
dictate
C=O
chemoselectivity
α,β-unsaturated
aldehyde,
which
verified
experimentally.
Our
mechanistic
study
may
help
design
homogeneous,
heterogeneous
biological
catalysts
reaction.
Russian Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
90(8), P. 895 - 1107
Published: April 20, 2021
The
interest
in
functional
supramolecular
systems
for
the
design
of
innovative
materials
and
technologies,
able
to
fundamentally
change
world,
is
growing
at
a
high
pace.
huge
array
publications
that
appeared
recent
years
global
literature
calls
systematization
structural
trends
inherent
formation
these
revealed
different
molecular
platforms
practically
useful
properties
they
exhibit.
attention
concentrated
on
topics
related
are
actively
explored
institutes
universities
Russia
last
10–15
years,
such
as
chemistry
host–guest
complexes,
crystal
engineering,
self-assembly
self-organization
solutions
interfaces,
biomimetics
machines
devices.
bibliography
includes
1714
references.
Natural Product Reports,
Journal Year:
2024,
Volume and Issue:
41(5), P. 748 - 783
Published: Jan. 1, 2024
This
review
covers
all
fungal
terpenoid
cyclases
(TCs),
including
class
I
and
II
TCs
as
well
emerging
UbiA-type
TCs,
together
with
their
tailoring
enzymes,
focusing
on
newly
identified
enzymes
from
2015
to
August
2023.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10979 - 10983
Published: April 8, 2024
It
has
been
widely
shown
that
water
microdroplets
have
a
plethora
of
unique
properties
are
highly
distinct
from
those
bulk
water,
among
which
an
especially
intriguing
one
is
the
strong
reducing
power
as
result
electrons
spontaneously
generated
at
air–water
interface.
In
this
study,
we
take
advantage
to
reduce
ortho-diiodotetrafluorobenzene
(o-C6F4I2)
into
C6F4I2•–
radical
anion.
Photoelectron
spectroscopy
and
density
functional
theory
computations
reveal
excess
electron
in
occupies
I–C1–C2–I
linkage,
elongates
C–I
bonds
but
surprisingly
shortens
C1–C2
bond,
making
bond
order
higher
than
double
similar
benzyne
molecule,
so
named
it
"quasi-benzyne".
The
anion
was
further
successfully
utilized
Diels–Alder
reaction,
typical
reaction
for
benzyne.
This
study
provides
good
example
strategically
utilizing
spontaneous
generating
exotic
anion,
anticipate
microdroplet
chemistry
can
be
avenue
rich
opportunities
new
catalyst-free
organic
reactions.
Natural Product Reports,
Journal Year:
2021,
Volume and Issue:
38(8), P. 1469 - 1505
Published: Jan. 1, 2021
Cytochrome
P450s,
laccases,
and
intermolecular
[4
+
2]
cyclases,
along
with
other
enzymes
were
utilized
to
catalyze
varied
dimerization
of
matured
natural
products
so
as
create
the
structural
diversity
complexity
in
microorganisms.
Natural Product Reports,
Journal Year:
2022,
Volume and Issue:
40(1), P. 89 - 127
Published: Sept. 20, 2022
Covering:
2010
to
2022Heterologous
expression
of
natural
product
biosynthetic
gene
clusters
(BGCs)
has
become
a
widely
used
tool
for
genome
mining
cryptic
pathways,
bottom-up
investigation
enzymes,
and
engineered
biosynthesis
new
variants.
In
the
field
fungal
products,
heterologous
complete
pathway
was
first
demonstrated
in
tenellin
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 18172 - 18183
Published: June 18, 2024
Crosstalk-oriented
chemical
evolution
of
natural
products
(NPs)
is
an
efficacious
strategy
for
generating
novel
skeletons
through
coupling
reactions
between
NP
fragments.
In
this
study,
two
NOD-like
receptor
protein
3
(NLRP3)
inflammasome
inhibitors,
sorbremnoids
A
and
B
(1
2),
with
unprecedented
architectures
were
identified
from
a
fungus
Penicillium
citrinum.
Compounds
1
2
exemplify
rare
instances
hybrid
NPs
formed
via
major
facilitator
superfamily
(MFS)-like
enzyme
by
reactive
intermediates
separate
biosynthetic
gene
clusters
(BGCs),
pcisor
pci56.
Both
are
NLRP3
inhibitors.
Sorbremnoid
demonstrated
strong
inhibition
IL-1β
directly
binding
to
the
protein,
inhibiting
assembly
activation
in
vitro,
potential
application
diabetic
refractory
wound
healing
suppression
excessive
inflammatory
responses.
This
research
will
inspire
development
anti-NLRP3
agents
as
lead
treatments
enhance
knowledge
pertaining
derived
crosstalk.