C-to-N atom swapping and skeletal editing in indoles and benzofurans
Nature,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 21, 2025
Abstract
Skeletal
editing
comprises
the
structural
reorganization
of
compounds.
Such
can
be
achieved
through
atom
swapping,
insertion,
deletion
or
compound’s
backbone
structure
1,2
.
Conducted
at
a
late
stage
in
drug
development
campaigns,
skeletal
enables
diversification
an
existing
pharmacophore,
enhancing
efficiency
development.
Instead
constructing
heteroarene
classically
from
basic
building
blocks,
variants
are
readily
accessible
directly
starting
lead
compound
approved
pharmacophore.
Here
we
present
C
to
N
swapping
indoles
C2
position
give
indazoles
oxidative
cleavage
indole
core
and
subsequent
ring
closure.
Reactions
proceed
ring-opened
oximes
as
intermediates.
These
deconstructed
intermediates
also
diverted
into
benzimidazoles
resulting
overall
with
concomitant
reorganization.
The
same
diverting
strategies
equally
well
applicable
benzofurans
leading
either
benzisoxazoles
benzoxazoles.
classes
obtained
these
methods—indazoles
3,4
,
5
6,7
benzoxazoles
8
—are
biologically
relevant
moieties
found
substructures
natural
products
pharmaceuticals.
procedures
introduced
substantially
enlarge
methods
portfolio
emerging
field
editing.
Язык: Английский
Transition Metal-Catalyzed Nitrogen Atom Insertion into Carbocycles
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 26, 2025
ConspectusN-Heterocycles
are
essential
in
pharmaceutical
engineering,
materials
science,
and
synthetic
chemistry.
Recently,
skeletal
editing,
which
involves
making
specific
point
changes
to
the
core
of
a
molecule
through
single-atom
insertion,
deletion,
or
transmutation,
has
gained
attention
for
its
potential
modify
complex
substrates.
In
this
context,
insertion
nitrogen
atoms
into
carbocycles
form
N-heterocycles
emerged
as
significant
research
focus
modern
chemistry
owing
novel
logic.
This
distinctive
retrosynthetic
approach
enables
late-stage
modification
molecular
skeletons
provides
different
pathway
synthesizing
multiply
substituted
N-heterocycles.
Nevertheless,
atom
proven
challenging
because
inherent
inertness
carbon-based
difficulty
cleaving
C-C
bonds.
Therefore,
selective
editing
remains
growing
field
Account
primarily
highlights
contributions
our
laboratory
active
acknowledges
key
from
other
researchers.
It
is
organized
two
sections
based
on
type
carbocycle.
The
first
section
explores
cycloalkenes.
Recent
Co-catalyzed
oxidative
azidation
strategies
have
enabled
cyclobutenes,
cyclopentenes,
cyclohexenes,
facilitating
synthesis
polysubstituted
pyridines,
been
conventionally
pyridine
cross-coupling.
subsequent
discovery
realm
arenes.
site-selective
stable
arenes
We
developed
method
intramolecular
benzene
rings
2-amino
biaryls
by
suppressing
competing
C-H
process
using
paddlewheel
dirhodium
catalyst.
addition,
address
issues
we
employed
arenols
substrates,
could
act
controlling
elements
editing.
reported
Cu-catalyzed
arenols,
proceeds
dearomative
azidation/aryl
migration
process,
enabling
incorporation
Inspired
result,
recently
extended
reaction
model
Fe-catalyst
facilitate
ring
contraction
nitrogen-inserted
product,
achieving
carbon-to-nitrogen
transmutation
arenols.
Various
polyaromatic
effectively
undergo
desired
atom's
presenting
considerable
various
applications
Account,
present
an
overview
achievements
reactions,
with
scopes,
mechanistic
features,
applications.
anticipate
that
will
provide
valuable
insights
propel
development
innovative
methodologies
both
N-heterocycle
synthesis.
Язык: Английский
Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4450 - 4459
Опубликована: Фев. 28, 2025
Enantioselective
electrocatalyzed
C–H
activations
have
emerged
as
a
transformative
platform
for
the
assembly
of
value-added
chiral
organic
molecules.
Despite
recent
progress,
construction
multiple
C(sp3)-stereogenic
centers
via
C(sp3)–C(sp3)
bond
formation
has
thus
far
proven
to
be
elusive.
In
contrast,
we
herein
report
an
annulative
activation
strategy,
generating
Fsp3-rich
molecules
with
high
levels
diastereo-
and
enantioselectivity.
κ2-N,O-oxazoline
preligands
were
effectively
employed
in
enantioselective
cobalt(III)-catalyzed
reactions.
Using
DFT-derived
descriptors
regression
statistical
modeling,
performed
parametrization
study
on
modularity
preligands.
The
resulted
model
describing
ligands'
selectivity
characterized
by
key
steric,
electronic,
interaction
behaviors.
Язык: Английский
Induced Circularly Polarized Luminescence From 0D Quantum Dots by 2D Chiral Nanosheets
Small,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 5, 2024
Abstract
Materials
with
circularly
polarized
luminescence
(CPL)
exhibit
great
application
potential
in
biological
scenes
such
as
cell
imaging,
optical
probes,
etc.
However,
most
developed
materials
are
non‐aqueous
and
toxic,
which
seriously
restricts
their
compatibility
the
life
systems.
Thus,
it
is
necessary
to
explore
a
water‐based
CPL
system
high
biocompatibility
so
that
promote
biologic
process.
Herein,
facile
efficient
route
achieve
properties
of
functional
aqueous
solution
demonstrated
by
combination
0D
quantum
dots
(QDs)
2D
chiral
nanosheets.
Benefited
specific
absorption
ability
nanosheets
for
left/right‐handed
CPL,
QDs
adsorbed
onto
surface
through
hydrogen
bond
interactions
showed
apparent
features.
In
addition,
this
has
good
extensibility
property
can
be
effectively
regulated
changing
kind
emissive
QDs.
More
importantly,
nano‐composite
fabrication
process
(one‐step
mixing)
suitable
real
applications,
undoubtedly
beneficial
further
progress
materials.
Язык: Английский
A Formal 1,2-Stevens Rearrangement of Thioester Ylides as a Single-Atom Molecular Editing Tool
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
A
rhodium-catalyzed
reaction
of
thioesters
with
diazo
reagents
was
recognized
as
a
powerful
and
unprecedented
tool
for
single-atom
molecular
editing
by
the
insertion
single
carbon
atom
into
C(O)─S
thioester
bond,
thereby
leading
to
various
α-thioketones
possessing
quaternary
atom.
selective
precise
defunctionalization
polyfunctionalized
products
further
demonstrated
synthetic
utility
synthesis
more
common
structural
classes
compounds.
Язык: Английский