Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(15), С. 2166 - 2183
Опубликована: Июль 12, 2024
ConspectusThe
Diels-Alder
reaction
is
well
known
as
a
concerted
[4
+
2]
cycloaddition
governed
by
the
Woodward-Hoffmann
rules.
Since
Prof.
Otto
Diels
and
his
student
Kurt
Alder
initially
reported
intermolecular
between
cyclopentadiene
quinone
in
1928,
it
has
been
recognized
one
of
most
powerful
chemical
transformations
to
build
C-C
bonds
construct
cyclic
structures.
This
named
widely
used
synthesizing
natural
products
drug
molecules.
Driven
synthetic
importance
reaction,
identifying
enzyme
that
stereoselectively
catalyzes
become
an
intriguing
research
area
product
biosynthesis
biocatalysis.
With
significant
progress
sequencing
bioinformatics,
dozens
Diels-Alderases
have
characterized
microbial
biosynthesis.
However,
few
are
evolutionally
dedicated
catalyzing
with
mechanism.This
Account
summarizes
our
endeavors
hunt
for
naturally
occurring
Diels-Alderase
from
plants.
Our
journey
started
biomimetic
syntheses
D-A-type
terpenoids
flavonoids,
showing
plants
use
both
nonenzymatic
enzymatic
cycloadditions
create
complex
Inspired
syntheses,
we
identify
hidden
biosynthetic
pathway
mulberry
Diels-Alder-type
cycloadducts
using
intermediate
probe-based
target
identification
strategy.
enzyme,
MaDA,
Natural Product Reports,
Год журнала:
2020,
Номер
37(12), С. 1627 - 1660
Опубликована: Янв. 1, 2020
This
review
article
highlights
recent
progress
on
their
sources,
bioactivities,
biosynthetic
hypotheses
and
total
chemical
syntheses
of
naturally
occurring
[4
+
2]
type
terpenoid
dimers.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(12), С. 5214 - 5225
Опубликована: Март 15, 2022
Achieving
convergent
synthetic
strategies
has
long
been
a
gold
standard
in
constructing
complex
molecular
skeletons,
allowing
for
the
rapid
generation
of
complexity
comparatively
streamlined
routes.
Traditionally,
biocatalysis
not
played
prominent
role
laboratory
synthesis,
with
application
biocatalysts
primarily
limited
to
synthesis
chiral
fragments.
Although
use
enzymes
enable
approaches
is
relatively
new
and
emerging,
combining
efficiency
transformations
selectivity
achievable
through
creates
opportunities
efficient
strategies.
This
Perspective
provides
an
overview
recent
developments
biocatalytic
offers
insights
into
advantages
these
methods
compared
their
small
molecule-based
counterparts.
Journal of Natural Products,
Год журнала:
2022,
Номер
85(3), С. 688 - 701
Опубликована: Фев. 2, 2022
The
implementation
of
ortho-quinone
methide
(o-QM)
intermediates
in
complex
molecule
assembly
represents
a
remarkably
efficient
strategy
designed
by
Nature
and
utilized
synthetic
chemists.
o-QMs
have
been
taken
advantage
biomimetic
syntheses
for
decades,
yet
relatively
few
examples
o-QM-generating
enzymes
natural
product
biosynthetic
pathways
reported.
that
discovered
thus
far
exhibit
tremendous
potential
biocatalytic
applications,
enabling
the
selective
production
desirable
compounds
are
otherwise
intractable
or
inherently
difficult
to
achieve
traditional
methods.
Characterization
this
machinery
has
shine
light
on
new
capable
similar
chemistry
diverse
substrates,
expanding
our
knowledge
Nature's
catalytic
repertoire.
presently
known
include
flavin-dependent
oxidases,
hetero-Diels–Alderases,
S-adenosyl-l-methionine-dependent
pericyclases,
α-ketoglutarate-dependent
nonheme
iron
enzymes.
In
review,
we
discuss
their
enzymatic
mechanisms
as
biocatalysts
constructing
molecules
such
cannabinoids.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(52), С. 23870 - 23878
Опубликована: Сен. 17, 2020
Tropolone
sesquiterpenoids
(TS)
are
an
intriguing
family
of
biologically
active
fungal
meroterpenoids
that
arise
through
a
unique
intermolecular
hetero
Diels-Alder
(hDA)
reaction
between
humulene
and
tropolones.
Here,
we
report
on
the
combinatorial
biosynthesis
series
unprecedented
analogs
TS
pycnidione
1
xenovulene
A
2.
In
systematic
synthetic
biology
driven
approach,
recombined
genes
from
three
biosynthetic
gene
clusters
(pycnidione
1,
2
eupenifeldin
3)
in
host
Aspergillus
oryzae
NSAR1.
Rational
design
reconstituted
pathways
granted
control
over
number
hDA
reactions
taking
place,
chemical
nature
fused
polyketide
moiety
(tropolono-
vs.
monobenzo-pyranyl)
degree
hydroxylation.
Formation
unexpected
monobenzopyranyl
was
investigated
using
isotope-feeding
studies
to
reveal
new
highly
unusual
oxidative
ring
contraction
rearrangement.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(15), С. 6006 - 6017
Опубликована: Апрель 7, 2021
The
sesquiterpene-tropolones
belong
to
a
distinctive
structural
class
of
meroterpene
natural
products
with
impressive
biological
activities,
including
anticancer,
antifungal,
antimalarial,
and
antibacterial.
In
this
article,
we
describe
concise,
modular,
cycloaddition-based
approach
series
sesquiterpene
mono-
bistropolones,
(−)-epolone
B,
(+)-isoepolone
(±)-dehydroxypycnidione,
(−)-10-epi-pycnidione.
Alongside
the
development
general
strategy
access
unique
family
metabolites
were
computational
modeling
studies
that
justified
diastereoselectivity
observed
during
key
cycloadditions.
Ultimately,
these
prompted
stereochemical
reassignments
pycnidione
subclass
shed
additional
light
on
biosynthesis
remarkable
products.
