Nature Chemistry,
Journal Year:
2024,
Volume and Issue:
16(5), P. 741 - 748
Published: Jan. 18, 2024
Abstract
Skeletal
editing
is
a
straightforward
synthetic
strategy
for
precise
substitution
or
rearrangement
of
atoms
in
core
ring
structures
complex
molecules;
it
enables
quick
diversification
compounds
that
not
possible
by
applying
peripheral
strategies.
Previously
reported
skeletal
common
arenes
mainly
relies
on
carbene-
nitrene-type
insertion
reactions
rearrangements.
Although
powerful,
efficient
and
applicable
to
late-stage
heteroarene
structure
modification,
these
strategies
cannot
be
used
pyridines.
Here
we
report
the
direct
pyridines
through
atom-pair
swap
from
CN
CC
generate
benzenes
naphthalenes
modular
fashion.
Specifically,
use
sequential
dearomatization,
cycloaddition
rearomatizing
retrocycloaddition
one-pot
sequence
transform
parent
into
bearing
diversified
substituents
at
specific
sites,
as
defined
reaction
components.
Applications
pyridine
cores
several
drugs
are
demonstrated.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(22), P. 12313 - 12370
Published: Nov. 9, 2023
Late-stage
functionalization
(LSF)
introduces
functional
group
or
structural
modification
at
the
final
stage
of
synthesis
natural
products,
drugs,
and
complex
compounds.
It
is
anticipated
that
late-stage
would
improve
drug
discovery's
effectiveness
efficiency
hasten
creation
various
chemical
libraries.
Consequently,
products
a
productive
technique
to
produce
product
derivatives,
which
significantly
impacts
biology
development.
Carbon-carbon
bonds
make
up
fundamental
framework
organic
molecules.
Compared
with
carbon-carbon
bond
construction,
activation
can
directly
enable
molecular
editing
(deletion,
insertion,
atoms
groups
atoms)
provide
more
efficient
accurate
synthetic
strategy.
However,
selective
unstrained
still
one
most
challenging
projects
in
synthesis.
This
review
encompasses
strategies
employed
recent
years
for
cleavage
by
explicitly
focusing
on
their
applicability
functionalization.
expands
current
discourse
reactions
providing
comprehensive
overview
types
bonds.
includes
C-C(sp),
C-C(sp2),
C-C(sp3)
single
bonds;
double
triple
bonds,
focus
catalysis
transition
metals
organocatalysts.
Additionally,
specific
topics,
such
as
ring-opening
processes
involving
three-,
four-,
five-,
six-membered
rings,
are
discussed,
exemplar
applications
these
techniques
showcased
context
bioactive
molecules
discovery.
aims
shed
light
advancements
field
propose
potential
avenues
future
research
realm
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2845 - 2854
Published: Jan. 18, 2024
In
this
report,
we
developed
a
unified
and
standardized
one-pot
sequence
that
converts
pyridine
derivatives
into
1,2-diazepines
by
inserting
nitrogen
atom.
This
skeletal
transformation
capitalizes
on
the
in
situ
generation
of
1-aminopyridinium
ylides,
which
rearrange
under
UV
light
irradiation.
A
thorough
evaluation
key
parameters
(wavelength,
reaction
conditions,
activating
agent)
allowed
us
to
elaborate
simple,
mild,
user-friendly
protocol.
The
model
was
extrapolated
more
than
40
examples,
including
drug
derivatives,
affording
unique
7-membered
structures.
Mechanistic
evidence
supports
transient
presence
diazanorcaradiene
species.
Finally,
pertinent
transformations
products,
ring
contraction
reactions
form
pyrazoles,
were
conducted
paved
way
broad
application
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4301 - 4308
Published: Feb. 9, 2024
The
development
of
divergent
methods
to
expedite
structure–activity
relationship
studies
is
crucial
streamline
discovery
processes.
We
developed
a
rare
example
regiodivergent
ring
expansion
access
two
regioisomers
from
common
starting
material.
To
enable
this
regiodivergence,
we
identified
distinct
reaction
conditions
for
transforming
oxindoles
into
quinolinone
isomers.
presented
proved
be
compatible
with
variety
functional
groups,
which
enabled
the
late-stage
diversification
bioactive
as
well
facilitated
synthesis
drugs
and
their
derivatives.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(32), P. 17570 - 17576
Published: Aug. 3, 2023
In
this
study,
we
describe
the
direct
insertion
of
an
intramolecular
nitrogen
atom
into
aromatic
C–C
bond.
transformation,
carbamoyl
azides
are
activated
by
a
Rh
catalyst
and
subsequently
directly
inserted
bond
arene
ring
to
access
fused
azepine
products.
This
transformation
is
challenging,
owing
existence
competitive
C–H
amination
pathway.
The
use
paddlewheel
dirhodium
complex
Rh2(esp)2
effectively
inhibited
undesired
insertion.
Density
functional
theory
calculations
were
performed
reveal
reaction
mechanism
origin
chemoselectivity
Rh-catalyzed
reactions.
novel
products
highly
robust
allow
for
downstream
diversification.
