Abstract
Transposition
reactions,
i.
e.,
switching
the
position
of
functional
groups,
are
a
powerful
tool
for
molecular
editing.
The
transposition
halogen
atom
attached
to
an
aromatic
ring,
referred
as
dance
reaction,
has
great
potential
in
fields
pharmaceuticals,
agrochemicals,
natural
products,
and
materials.
However,
substrate
scope
this
reaction
is
limited
owing
intrinsic
difficulty
facilitating
multiple
catalytic
cycles
involving
several
aryllithium
species.
In
concept
paper,
recent
advances
catalysis
that
have
expanded
highlighted.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 2939 - 2943
Опубликована: Янв. 12, 2024
A
practical
method
for
the
synthesis
of
15N-labeled
azines
with
a
high
degree
isotopic
enrichment
is
described.
Activation
azine
heterocycles
an
electron-deficient
arene
allows
facile
substitution
nitrogen
atom
specifically
designed
reagent
that
undergoes
canonical
ANRORC-type
mechanism.
wide
range
can
be
converted
to
their
corresponding
15N
isotopologs
using
this
method,
and
it
also
dearomative
access
reduced
heterocyclic
congeners.
short
formal
15N-solifenacin
accomplished
as
well
demonstrate
application
generating
labeled
pharmaceuticals.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 2944 - 2949
Опубликована: Янв. 16, 2024
Methods
to
incorporate
stable
radioisotopes
are
integral
pharmaceutical
and
agrochemical
development.
However,
despite
the
prevalence
of
pyridines
in
candidate
compounds,
methods
15N
atoms
within
their
structures
limited.
Here,
we
present
a
general
approach
pyridine
15N-labeling
that
proceeds
via
ring-opening
NTf-Zincke
imines
then
ring-closure
with
commercially
available
15NH4Cl
salts.
This
process
functions
on
range
substituted
pyridines,
from
simple
building
block-type
compounds
late-stage
labeling
complex
pharmaceuticals,
15N-incorporation
is
>95%
most
cases.
The
reactivity
Zincke
imine
intermediates
also
enables
deuteration
C3-
C5-positions,
resulting
higher
mass
isotopologs
required
for
LCMS
analysis
biological
fluids
during
drug
Science,
Год журнала:
2024,
Номер
386(6717), С. 99 - 105
Опубликована: Окт. 3, 2024
The
identity
of
a
heteroatom
within
an
aromatic
ring
influences
the
chemical
properties
that
heterocyclic
compound.
Systematically
evaluating
effect
single
atom,
however,
poses
synthetic
challenges,
primarily
as
result
thermodynamic
mismatches
in
atomic
exchange
processes.
We
present
photocatalytic
strategy
swaps
oxygen
atom
furan
with
nitrogen
group,
directly
converting
into
pyrrole
analog
intermolecular
reaction.
High
compatibility
was
observed
various
derivatives
and
nucleophiles
commonly
used
drug
discovery,
late-stage
functionalization
furnished
otherwise
difficult-to-access
pyrroles
from
naturally
occurring
furans
high
molecular
complexity.
Mechanistic
analysis
suggested
polarity
inversion
through
electron
transfer
initiates
redox-neutral
processes
at
room
temperature.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
We
recently
reported
a
chiral
phosphoric
acid
(CPA)
catalyzed
enantioselective
photomediated
ring
contraction
of
piperidines
and
other
saturated
heterocycles.
By
extruding
single
heteroatom
from
ring,
this
transformation
builds
desirable
C(sp3)–C(sp3)
bonds
in
the
contracted
products;
however,
origins
enantioselectivity
remain
poorly
understood.
In
work,
has
been
explored
across
an
expanded
structurally
diverse
substrate
scope,
revealing
wide
range
enantioselectivities
(0–99%)
using
two
distinct
CPA
catalysts.
Mechanistic
investigations
support
rate-determining
excitation
that
generates
short-lived
achiral
intermediates
are
intercepted
by
enantiodetermining
closure.
The
effects
competitive
uncatalyzed
reactivity
light-driven
reversibility
closure
on
have
elucidated.
Statistical
models
were
built
regressing
scope
against
key
structural
features
products
for
both
resultant
suggested
factors
influence
response
each
catalyst
enabled
rational
modification
pharmaceutically
relevant
target
molecule
to
improve
enantioselectivity.
Finally,
density
functional
theory
(DFT)-based
transition
state
analysis
identified
noncovalent
interactions
with
correlated
unique
selectivity-relevant
uncovered
through
statistical
modeling.
Our
findings
not
only
offer
comprehensive
insight
into
system
but
should
also
aid
future
development
related
CPA-catalyzed
reactions.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(32), С. 22829 - 22839
Опубликована: Авг. 1, 2024
The
molecular
editing
of
ketones
represents
an
appealing
strategy
due
to
its
ability
maximize
the
structural
diversity
ketone
compounds
in
a
straightforward
manner.
However,
developing
efficient
methods
for
arbitrary
modification
ketonic
molecules,
particularly
those
integrated
within
complex
skeletons,
remains
significant
challenge.
Herein,
we
present
unique
recasting
that
involves
radical
acylation
Chem,
Год журнала:
2024,
Номер
10(6), С. 1940 - 1949
Опубликована: Июнь 1, 2024
The
skeletal
editing
of
heteroarenes
introduces
new
disconnections
to
the
chemistry
lexicon,
enabling
interconversion
ring
systems
via
selective
breaking/re-making
carbon
framework.
We
describe
one-pot
transformation
pyridines
into
benzene
derivatives,
using
a
nucleophilic
addition
ring-opening/ring-closing
(ANRORC)
process
with
soft
nucleophiles
such
as
malonate.
Triflic
anhydride
activates
pyridine
ANRORC
synthesis
an
isolable
amine
intermediate,
which
aromatizes
on
simple
heating.
reaction
has
been
exemplified
room
temperature
protocol,
along
direct
syntheses
drug-like,
tertiary-alkylated,
and
isotopically
labeled
benzoates.
Organic Letters,
Год журнала:
2024,
Номер
26(20), С. 4280 - 4285
Опубликована: Май 13, 2024
Reactions
that
change
the
identity
of
an
atom
within
a
ring
system
are
emerging
as
valuable
tools
for
site-selective
editing
molecular
structures.
Herein,
we
describe
expansion
underdeveloped
transformation
directly
converts
azaarene-derived
N-oxides
to
all-carbon
arenes.
This
transmutation
exhibits
good
functional
group
tolerance
and
replaces
N-oxide
moiety
with
either
unsubstituted,
substituted,
or
isotopically
labeled
carbon
atoms
in
single
laboratory
operation.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 4, 2024
Abstract
Developing
skeletal
editing
tools
is
not
a
trivial
task,
and
realizing
the
corresponding
single-atom
transmutation
in
ring
system
without
altering
size
even
more
challenging.
Here,
we
introduce
strategy
that
enables
polycyclic
arenols,
highly
prevalent
motif
bioactive
molecules,
to
be
readily
converted
into
N
-heteroarenes
through
carbon–nitrogen
transmutation.
The
reaction
features
selective
nitrogen
insertion
C–C
bond
of
arenol
frameworks
by
azidative
dearomatization
aryl
migration,
followed
ring-opening,
ring-closing
(ANRORC)
achieve
carbon-to-nitrogen
aromatic
framework
arenol.
Using
widely
available
arenols
as
-heteroarene
precursors,
this
alternative
approach
allows
streamlined
assembly
complex
heteroaromatics
with
broad
functional
group
tolerance.
Finally,
pertinent
transformations
products,
including
synthesis
biheteroarene
skeletons,
were
conducted
exhibited
significant
potential
materials
chemistry.
