Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 27, 2024
Abstract
Kalmanol
(
1
)
is
the
first
isolated
kalmane‐type
grayanoid
featuring
a
highly
oxidized
5/8/5/5
tetracyclic
carbon
skeleton
and
9
contiguous
stereocenters.
We
have
accomplished
efficient
asymmetric
total
synthesis
of
in
16
steps
from
known
compounds
(20
commercially
available
starting
materials)
by
modular
synthetic
strategy.
A
intermediate
was
prepared
convergent
manner
through
Grignard
reaction
subsequent
ring‐closing
metathesis
two
enantiomerically
enriched
fragments.
The
polyhydroxy
groups
were
introduced
late‐stage
stereo‐
regioselective
oxidations.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Фев. 23, 2024
We
have
accomplished
the
first
and
asymmetric
total
synthesis
of
principinol
B,
a
grayanoid
possessing
an
oxabicyclo[3.2.1]
architecture.
A
functionalized
5/7/6/5
tetracyclic
intermediate
was
assembled
in
convergent
manner
by
diastereoselective
intermolecular
aldol
reaction
subsequent
carbonyl-olefin
metathesis
two
enantiomerically
enriched
fragments.
The
architecture
containing
6,10-ether
bridge
constructed
Williamson
ether
synthesis.
RSC Advances,
Год журнала:
2025,
Номер
15(6), С. 4496 - 4525
Опубликована: Янв. 1, 2025
This
review
covers
recent
advancements
in
Diels–Alder
reaction
chemistry
for
total
synthesis
of
Natural
Products
(2020–2023)
and,
where
relevant,
discusses
key
structural
features
and
biological
activity
bioactive
natural
products.
Organic Letters,
Год журнала:
2024,
Номер
26(17), С. 3524 - 3529
Опубликована: Апрель 24, 2024
A
ring
distortion
approach
for
the
synthesis
of
an
advanced
intermediate
en
route
to
rhodomolleins
XIV
and
XLII
was
described,
which
led
successful
construction
5/8/5/5
tetracyclic
core
framework
kalmane
diterpenoids.
Key
steps
strategy
include
oxidative
dearomatization-induced
(ODI)-Diels-Alder
cycloaddition,
a
Dowd-Beckwith
rearrangement,
bioinspired
Wagner-Meerwein
rearrangement.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 27, 2024
ConspectusCurrently,
the
frontier
challenges
in
total
synthesis
pertain
to
increasing
synthetic
efficiency
and
enabling
divergent
of
a
number
natural
products.
Bioinspired
has
been
well
recognized
as
an
effective
approach
efficiency.
Especially,
when
bioinspired
was
applied
at
late-stage
skeletal
diversification
generate
various
products
with
distinct
carbon
skeletons,
it
held
special
promise
for
achieving
both
goals.
In
our
laboratory,
served
one
two
long-standing
principles
facilitating
efficient
this
Account,
we
summarize
endeavors
journeys
We
categorize
work
into
three
parts
based
on
imitation
biosynthetic
reactions
processes.(1)
To
mimic
key
cyclization
steps.
Inspired
by
process
that
formed
core
skeleton,
developed
new
methods
enable
rapid
construction
skeletons
targeted
molecules,
ultimately
leading
their
concise
synthesis,
example,
seven-step
lamellarins
D
H
featuring
oxidative
coupling
reactions,
clavicipitic
acid
highlighted
C-H
activation/aminocyclization
cascade
reaction,
eight-step
phalarine
via
coupling,
α-cyclopiazonic
acid,
ten-step
speradine
C
through
reaction
initiated
benzylic
carbocation
indole.
(2)
revised
pathway
proposed
us.
some
cases,
processes
may
be
flawed,
they
contradict
basic
chemistry.
Thus,
alternative
must
investigated.
showcase
euphorikanin
A
benzilic
acid-type
rearrangement
bipolarolides
B
Prins
reaction/ether
formation
cyclization.
(3)
process.
Nature
usually
synthesizes
multitude
from
common
intermediate
manner.
Biogenic
also
drawn
attention.
Compared
single-target-oriented
skeletal-diversity-oriented
remains
underexplored
due
its
high
challenges.
showcased
syntheses
ten
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 31, 2024
Kalmanol,
the
flagship
member
of
kalmane
diterpene
family,
possesses
a
complex
and
highly
oxidized
5/5/8/5
tetracyclic
skeleton
with
nine
contiguous
stereocenters
exhibits
significant
analgesic
effects
cardiotoxic
properties.
We
have
achieved
efficient
total
synthesis
(+)-kalmanol
in
22
steps
2.3
%
yield.
The
featured
Rh-catalyzed
[5+2+1]
cycloaddition
reaction
to
construct
5/5/8
tricyclic
skeleton,
meticulously
designed
sequence
stereoselective
oxidations
skeleton.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(59)
Опубликована: Авг. 14, 2024
The
past
few
decades
have
witnessed
tremendous
development
within
epoxides.
Among
the
many
known
reactions
involving
epoxide,
Meinwald
rearrangements
represent
one
of
most
important
and
attractive
approaches,
which
can
transform
epoxides
into
versatile
carbonyl
compounds.
Given
high
efficiency
this
protocol,
substantial
efforts
been
made
by
researchers
utilizing
multiple
catalyst
systems.
This
review
provides
an
overview
recent
advances
in
rearrangement
(from
2014
onward),
along
with
detailed
discussions
on
mechanistic
insights.
aims
to
highlight
importance
value
these
methodologies,
thereby
promoting
further
investigation
application.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 3, 2025
Comprehensive
Summary
Natural
products
with
high
oxidation
states
and
complex
chemical
skeletons
exhibit
diverse
bioactivities
due
to
their
unique
interactions
biological
targets.
The
state
is
characterized
by
the
presence
of
multiple
oxygen‐containing
functional
groups
such
as
hydroxyl
groups,
carbonyl
epoxides
that
are
usually
tough
construct
selectively.
In
recent
years,
thanks
development
efficient
strategies
sophisticated
methodologies,
significant
advancements
have
been
made
in
total
syntheses
highly
oxidized
natural
(HONPs).
this
review,
we
highlight
examples
HONPs
focusing
on
tetrodotoxin
(TTX)
its
derivatives,
steroidal
alkaloids,
sesquiterpenes,
diterpenoids
since
2019.
Key
Scientists
2005,
Yang
group
applied
thioureas
ligands
Pauson−Khand
reaction
for
synthesis
triterpene
products.
methodological
advances
achieved
a
series
topologically
structural
features
following
years.
2009,
Baran
established
pioneering
“two‐phase”
approach
terpenes,
an
innovative
strategy
has
inspired
numerous
field.
2011,
Xu
Theodorakis
(−)‐jiadifenolide,
sesquiterpene
from
Illicium
.
2012,
Li
6π
electrocyclization
containing
aromatic
rings.
2014,
Inoue
introduced
α‐alkoxy
bridgehead
radical,
facilitating
unified
ryanodane
diterpenoids.
subsequent
radical‐based
convergent
were
employed
assembling
HONPs.
developed
type
ΙΙ
[5+2]
reaction,
which
can
be
efficiently
featuring
bridged
ring
systems.
Reisman
presented
pattern
analysis
guided
synthetic
designs
complex,
isoryanodane
diterpenes.
2017,
Gao
reported
photoenolization/Diels‐Alder
(PEDA)
constructing
related
polycyclic
rings
elevated
states.
2018,
Ding
unprecedented
oxidative
dearomatization‐induced
(ODI)
cycloaddition/pinacol‐
1,2‐acyl
migration
cascade
assemble
oxygenated
bicyclo[3.2.1]octane
system,
was
subsequently
grayanane
same
year,
Gui
explored
“bioinspired”
strategic
transformations
enabled
rapid
construction
core
framework
steroid
terpenoid
2020,
Luo
successfully
synthesized
several
HONPs,
including
(−)‐batrachotoxinin,
(−)‐zygadenine,
diterpenoids,
employing
elegant
strategies.
2021,
Zhang
site‐specific
photochemical
desaturation
late‐stage
skeletal
reorganization
strategies,
enabling
divergent
sesquiterpenes.
2022,
Jia
first
(−)‐principinol
C,
accomplished
six
More
recently,
Trauner
concise
tetrodotoxin,
particularly
strategy.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(19), С. 15963 - 15969
Опубликована: Апрель 29, 2025
The
first
total
synthesis
of
the
sesterterpenoid
(-)-calidoustene
has
been
accomplished,
featuring
a
stereoselective
Michael/aldol
cascade
to
construct
trans-hydrindane
backbone,
tandem
Pummerer/Sakurai
cyclization
establish
bicyclo[3.2.1]octane
framework,
metallaphotoredox
enone
coupling
followed
by
MHAT-initiated
forge
congested
central
C-ring,
and
late-stage
functionalization
via
Cu-catalyzed
desaturation
diimide
reduction.
