Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
21(4), С. 775 - 782
Опубликована: Дек. 19, 2022
A
rhodium-catalyzed
formal
[4
+
1]-cyclization
reaction
of
aryl
substituted
pyrazoles
with
cyclopropanols
via
C-H
bond
activation/cyclization
processes
to
selectively
construct
a
series
carbonyl
functionalized
pyrazolo[5,1-a]isoindoles
is
described.
The
features
good
functional
group
compatibility
and
broad
substrate
scope
respect
both
cyclization
components
up
84%
yields.
Mechanistic
studies
indicated
that
the
cleavage
might
be
rate-determining
step
in
this
transformation.
Green Chemistry,
Год журнала:
2023,
Номер
25(5), С. 1975 - 1981
Опубликована: Янв. 1, 2023
This
study
describes
a
green
and
sustainable
photoinduced
strategy
for
decarboxylative
C–H
(amino)alkylation
of
heteroarenes
with
carboxylic
acids
under
metal-
photosensitizer-free
conditions.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5122 - 5129
Опубликована: Янв. 1, 2024
This
study
demonstrates
a
strategy
involving
photoinduced
energy
transfer
for
decarboxylative
Minisci
C–H
(amino)alkylation
of
heteroarenes
employing
diverse
oxime
esters
(from
carboxylic
acids)
as
(amino)alkylating
reagents.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(14)
Опубликована: Янв. 20, 2024
Abstract
Although
photocatalytic
C−H
activation
has
been
realized
by
using
heterogeneous
catalysts,
most
of
them
require
high‐temperature
conditions
to
provide
the
energy
required
for
bond
breakage.
The
catalysts
with
photothermal
conversion
properties
can
catalyze
this
reaction
efficiently
at
room
temperature,
but
so
far,
these
have
rarely
developed.
Here,
we
construct
bifunctional
Rh‐COF‐316
and
‐318
combine
photosensitive
covalent
organic
frameworks
(COFs)
transition‐metal
catalytic
moiety
a
post‐synthetic
approach.
Rh‐COF
enable
first
time,
exhibit
excellent
yields
(up
98
%)
broad
scope
substrates
in
[4+2]
annulation
while
maintaining
high
stability
recyclability.
Significantly,
work
is
highest
yield
reported
far
porous
materials
catalyzing
C(sp
2
)−C(sp
)
formation
temperature.
performances
be
attributed
COF‐316,
which
enhances
effect
(Δ
T
=50.9
°C),
thus
accelerating
exchange
catalyst
substrates.
Organic Letters,
Год журнала:
2024,
Номер
26(16), С. 3332 - 3337
Опубликована: Апрель 15, 2024
As
a
class
of
rising
electrophilic
coupling
reagents,
aryl–thianthreniums
(aryl-TTs)
have
been
gaining
immense
attention.
Herein,
novel
palladium-catalyzed
domino
annulation
aryl-TTs
with
anhydrides
is
proposed
to
rapidly
assemble
collection
highly
functionalized
fluorenones.
This
finding
presents
an
innovative
reaction
pattern
wherein
the
version
first
involved.
Heavily
compared
existing
conversions
aryl-TTs,
this
identified
process
successively
functions
as
four
aryl
C–H
bonds.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 26, 2025
Regiodivergent
C-C
bond-forming
reactions
are
a
powerful
tool
for
constructing
diverse
molecular
architectures
from
common
precursors.
While
transition
metal
catalysis
has
dominated
regioselective
transformations,
achieving
similar
precision
with
transition-metal-free
methods
remains
an
unmet
challenge,
particularly
when
using
identical
starting
materials.
In
this
work,
we
report
transition-metal-free,
regiodivergent
direct
alkylation
of
electronically
unbiased
pyridines
1,1-diborylalkanes
as
the
sole
alkylating
agent.
The
key
to
controlling
regioselectivity
lies
in
choice
alkyllithium
activator
1,1-diborylalkanes:
methyllithium
directs
predominantly
C4
position,
while
sec-butyllithium
promotes
C2-alkylation.
Mechanistic
studies
reveal
that
structural
dynamics
clusters
dictate
regioselectivity,
tetrameric
favoring
C4-alkylation
and
dimeric
preferring
This
method
demonstrates
broad
substrate
scope,
enables
late-stage
functionalization
complex
molecules,
allows
sequential
installation
two
distinct
alkyl
groups
onto
pyridine
scaffold.
Our
approach
provides
versatile
site-selective
functionalization,
offering
new
possibilities
synthesizing
alkylated
pharmaceutical
materials
research.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(32), С. 6293 - 6313
Опубликована: Янв. 1, 2022
As
one
of
the
most
important
structural
units
in
pharmaceuticals
and
medicinal
chemistry,
quinazolinone
its
derivatives
exhibit
a
wide
range
biological
pharmacological
activities,
including
anti-inflammatory,
antitubercular,
antiviral,
anticancer
etc.
In
particular,
2,3-fused
quinazolinones
have
attracted
much
attention
because
rings
fused
to
2,3-positions
improve
their
rigidity
planarity.
Their
synthetic
strategies
made
great
advances
recent
years.
Therefore,
this
review
focuses
on
novel
for
synthesis
from
2017
2022,
such
as
difunctionalization
alkenes,
ring-opening
easily
available
small
rings,
dehydrogenative
cross-coupling
reactions,
transition-metal
catalyzed
cyclizations,
cycloadditions,
other
cascade
reactions.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4042 - 4052
Опубликована: Март 16, 2023
The
development
of
ligands
and
the
elucidation
their
roles
in
catalytic
cycle
are
key
to
achieving
high
efficiency
selectivity
nondirected
transition-metal-catalyzed
C–H
functionalization.
In
particular,
careful
ligand
design
can
enable
functionalization
previously
inaccessible
substrate
positions,
which
lead
regiodivergent
transformations
common
reactants.
this
study,
a
series
pyrazolopyridone
(PzPyOH)
that
be
easily
prepared
single
step
was
developed
for
Pd-catalyzed
perdeuteration
meta-selective
alkenylation
arenes.
system,
2-pyridone
moiety
incorporated
function
as
an
internal
base,
facilitating
cleavage
rendering
activation
reversible,
even
at
challenging
sp2
bonds,
thus
enabling
perdeuteration.
addition,
reversible
bonds
implies
site
is
determined
during
migratory
insertion
reaction,
thereby
preferentially
functionalizing
meta-positions
rather
than
typically
more
reactive
ortho-
para-positions
anisole
derivatives.
Further,
electronic
structural
properties
pyrazole
provide
flexibility
binding
Pd,
facile
coordination
alkene
coupling
partner
alkenylation.
process,
hydrogen
bonding
between
pyridone
acetate
crucial
stabilize
intermediates,
allowing
different
types
modes,
including
L,L-
L,X-type
bidentate
monodentate
binding.
Kinetic
computational
studies
support
proposed
mechanisms
alkenylation,
findings
reveal
factors
functionalization,
will
useful
further
pyrazole-
pyridone-containing
transition
metal
catalysis.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(14)
Опубликована: Янв. 20, 2024
Abstract
Although
photocatalytic
C−H
activation
has
been
realized
by
using
heterogeneous
catalysts,
most
of
them
require
high‐temperature
conditions
to
provide
the
energy
required
for
bond
breakage.
The
catalysts
with
photothermal
conversion
properties
can
catalyze
this
reaction
efficiently
at
room
temperature,
but
so
far,
these
have
rarely
developed.
Here,
we
construct
bifunctional
Rh‐COF‐316
and
‐318
combine
photosensitive
covalent
organic
frameworks
(COFs)
transition‐metal
catalytic
moiety
a
post‐synthetic
approach.
Rh‐COF
enable
first
time,
exhibit
excellent
yields
(up
98
%)
broad
scope
substrates
in
[4+2]
annulation
while
maintaining
high
stability
recyclability.
Significantly,
work
is
highest
yield
reported
far
porous
materials
catalyzing
C(sp
2
)−C(sp
)
formation
temperature.
performances
be
attributed
COF‐316,
which
enhances
effect
(Δ
T
=50.9
°C),
thus
accelerating
exchange
catalyst
substrates.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 15, 2024
A
molecular
editing
reaction
for
converting
pyrrole
rings
into
benzene
through
a
sequential
pathway
of
Diels-Alder
and
cheletropic
reactions
was
developed.
The
nitrogen
atom
in
N-bridged
intermediate
is
eliminated
the
form
N
