Angewandte Chemie,
Год журнала:
2023,
Номер
135(25)
Опубликована: Апрель 26, 2023
Abstract
Carbazole
alkaloids
hold
great
potential
in
pharmaceutical
and
material
sciences.
However,
the
current
approaches
for
C1
functionalization
of
carbazoles
rely
on
use
a
pre‐installed
directing
group,
severely
limiting
their
applicability
hindering
overall
efficiency.
Herein,
we
report
first
time
development
direct
Pd‐catalyzed
C−H
alkylation
acylation
assisted
by
norbornene
(NBE)
as
transient
mediator.
Notably,
involvement
six‐membered
palladacycle
intermediate
was
suggested
this
case,
representing
example
such
intermediacy
within
extensively
studied
Pd/norbornene
reactions
realm.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 9512 - 9518
Опубликована: Март 29, 2024
1,2-Azaborines,
a
unique
class
of
BN-isosteres
benzene,
have
attracted
great
interest
across
several
fields.
While
significant
advancements
been
made
in
the
postfunctionalization
1,2-azaborines,
challenges
still
exist
for
selective
functionalization
C4
position
and
access
to
1,2-azaborines
with
five
or
six
independently
installed
substituents.
Here
we
report
rapid
modular
method
C3
difunctionalization
using
palladium/norbornene
(Pd/NBE)
cooperative
catalysis.
Enabled
by
C2
amide-substituted
NBE,
diverse
3-iodo-1,2-azaborines
can
be
used
as
substrates,
showing
broad
functional
group
tolerance.
Besides
Chemical Society Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Differentiating
between
two
highly
similar
C-H
bonds
in
a
given
molecule
remains
fundamental
challenge
synthetic
organic
chemistry.
Directing
group
assisted
strategies
for
the
functionalisation
of
proximal
has
been
known
last
few
decades.
However,
distal
bond
is
strenuous
and
requires
distinctly
specialised
techniques.
In
this
review,
we
summarise
advancement
Pd-catalysed
C(sp
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 26, 2023
Carbazole
alkaloids
hold
great
potential
in
pharmaceutical
and
material
sciences.
However,
the
current
approaches
for
C1
functionalization
of
carbazoles
rely
on
use
a
pre-installed
directing
group,
severely
limiting
their
applicability
hindering
overall
efficiency.
Herein,
we
report
first
time
development
direct
Pd-catalyzed
C-H
alkylation
acylation
assisted
by
norbornene
(NBE)
as
transient
mediator.
Notably,
involvement
six-membered
palladacycle
intermediate
was
suggested
this
case,
representing
example
such
intermediacy
within
extensively
studied
Pd/norbornene
reactions
realm.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(12), С. 3333 - 3340
Опубликована: Янв. 1, 2024
We
report
a
Pd/NBE
cooperative
catalyzed
ortho
C–H
methylation
and
trideuteromethylation
of
arylthianthrenium
salts,
enabling
the
efficient
synthesis
wide
variety
(trideutero)methylated
arenes
in
moderate
to
good
yields.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(43)
Опубликована: Сен. 6, 2023
Abstract
Methods
that
can
simultaneously
install
multiple
different
functional
groups
to
heteroarenes
via
C−H
functionalizations
are
valuable
for
complex
molecule
synthesis,
which,
however,
remain
challenging
realize.
Here
we
report
the
development
of
vicinal
di‐carbo‐functionalization
indoles
in
a
site‐
and
regioselective
manner,
enabled
by
palladium/norbornene
(Pd/NBE)
cooperative
catalysis.
The
reaction
is
initiated
Pd(II)‐mediated
C3‐metalation
specifically
promoted
C1‐substituted
NBEs.
mild,
scalable,
robust
conditions
allow
good
substrate
scope
excellent
group
tolerance.
resulting
C2‐arylated
C3‐alkenylated
be
converted
diverse
synthetically
useful
scaffolds.
combined
experimental
computational
mechanistic
study
reveals
unique
role
NBE
accelerating
turnover‐limiting
oxidative
addition
step.
ACS Catalysis,
Год журнала:
2024,
Номер
14(10), С. 7762 - 7770
Опубликована: Май 3, 2024
The
4-aryl-2-pyridone
scaffold
is
considered
to
be
a
privileged
pharmacophore.
Diversity-oriented
synthesis
of
its
derivatives
pressing
demand
within
the
field
medicinal
chemistry.
Herein,
we
report
site-selective
C–H
arylation
2-pyridones
via
palladium/norbornene
cooperative
catalysis.
success
this
research
based
on
nucleophilicity
and
metalation
properties
exhibited
by
C5
position
in
2-pyridones,
an
activated
norbornene
that
was
employed
capture
C5-palladation
intermediate
transfer
it
C4
position,
resulting
highly
specific
at
position.
This
methodology
showcases
remarkable
compatibility
with
readily
available
aryl
bromides,
enabling
efficient
diverse
range
functional
scaffolds
(46
examples)
notable
site
selectivity,
which
will
very
useful
drug
discovery.
Furthermore,
approach
successfully
utilized
for
economically
viable
perlolidine
analogues.
Density
theory
calculations
revealed
preference
bond
activation
2-pyridones.
In
addition,
insights
into
mechanism
suggest
oxidative
addition
reductive
elimination
bromides
are
crucial
steps
conversion.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 7, 2024
Abstract
Site‐selective
ortho/ipso
C−H
difunctionalizations
of
aromatic
compounds
were
designed
to
afford
polyfunctionalized
arenes
including
challenging
1,2,3,4‐tetrasubstituted
ones
(62
examples,
up
97
%
yields).
To
ensure
the
excellent
regioselectivity
process
while
keeping
high
efficiency,
an
original
strategy
based
on
a
“C−H
thianthenation/Catellani‐type
reaction”
sequence
was
developed
starting
from
simple
arenes.
Non‐prefunctionalized
first
regioselectively
converted
into
corresponding
thianthrenium
salts.
Then,
palladium‐catalyzed,
norbornene
(NBE)‐mediated
allowed
synthesis
ipso
‐olefinated/
ortho
‐alkylated
using
thianthrene
as
leaving
group
(revisited
Catellani
reaction).
Pleasingly,
commercially
available
(NBE)
and
unique
catalytic
system,
synthetic
challenges
known
for
reaction
with
aryl
iodides
smoothly
successfully
tackled
“thianthrenium”
approach.
The
protocol
robust
(gram‐scale
reaction)
widely
applied
two‐fold
functionalization
various
bio‐active
compounds.
Moreover,
panel
olefins
alkyl
halides
coupling
partners
suitable.
further
incorporation
other
groups
at
(CN/alkyl/H,
aryl)
(alkyl,
aryl,
amine,
thiol)
positions,
showcasing
generality
process.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 9, 2024
In
this
work,
we
describe
an
efficient
and
modular
method
for
enantiodivergent
accessing
P(V)-stereogenic
molecules
by
utilizing
the
catalytic
atroposelective
Catellani-type
C-H
arylation/desymmetric
intramolecular
N-arylation
cascade
reaction.
The
enantioselectivity
of
protocol
was
proved
to
be
tuned
polarity
solvent,
thus
providing
a
wide
range
both
chiral
enantiomers
in
moderate
good
yields
with
excellent
enantiomeric
excesses.
Noteworthy
is
that
strategy
developed
herein
represents
unprecedented
example
solvent-dictated
inversion
compounds.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18855 - 18860
Опубликована: Июль 1, 2024
Synthesis
of
interior-functionalized
dendritic
macromolecules
is
generally
tedious
and
labor-intensive,
which
has
been
a
key
factor
hampering
their
practical
applications.
Here,
we
have
revisited
this
long-standing
challenge
devised
modular
convergent
platform
to
synthesize
multifunctional
dendrons
with
all-carbon
backbones
up
four
generations
via
an
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12181 - 12191
Опубликована: Июль 30, 2024
The
advancement
of
sophisticated
synthetic
methodologies
that
streamline
reaction
processes
while
enhancing
molecular
complexity
is
a
perpetual
necessity
in
the
realm
chemistry.
Catalytic
one-pot
cascade
play
crucial
role
efficient
construction
intricate
molecules
with
exceptional
chemoselectivity.
Herein,
we
present
approach
for
synthesis
polycyclic
fused
δ-lactams
via
sequential
phosgenation,
Pd/NBE-catalyzed
ortho-carbamoylation/ipso-Heck-type
cyclization,
and
C–H
activation
from
readily
available
aryl
halides,
amines,
triphosgenes.
This
stands
out
as
first
example
situ
carbamoyl
chloride
formation
amine
precursors,
presenting
an
alternative
to
existing
transformations
involving
chlorides.
practical
significance
these
showcased
by
81
rapid
economically
favorable
manner,
without
need
intermediate
purification.
Moreover,
were
scalable
compatible
various
natural
products
pharmaceuticals,
further
underscoring
effectiveness
this
strategy.
relatively
rigid
coplanar
structure
displayed
our
synthesized
exhibits
distinct
room-temperature
phosphorescence
characteristics,
which
have
been
utilized
anticounterfeiting
high-security-level
data
encryption.
