Synlett,
Год журнала:
2023,
Номер
35(08), С. 851 - 861
Опубликована: Ноя. 24, 2023
Abstract
Base
metal
catalyzed
C–H
activation
represents
a
highly
atom
economic
method
to
access
functionalized
molecules.
This
Account
will
focus
on
Ni-catalyzed
of
sp3-hybridized
carbon
atoms
with
particular
mechanism,
recent
applications,
challenges,
and
outlook
in
this
area.
primarily
mechanistic
work
from
2017–2023.1
Metal
Activation
2
Nickel-Catalyzed
sp3
3
Differences
between
Ni
Pd
4
Mechanistic
Considerations
5
Elementary
Steps
6
Directed
7
Choice
Directing
Group
8
Primary
9
Secondary
10
Tertiary
11
Conclusion
Outlook
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.
Organometallics,
Год журнала:
2023,
Номер
42(21), С. 3164 - 3172
Опубликована: Ноя. 1, 2023
A
general
method
for
the
Ni-catalyzed
Buchwald–Hartwig
amination
of
(hetero)aryl
chlorides
using
both
anilines
and
aliphatic
amines
under
homogeneous
conditions
has
been
developed.
Key
to
success
this
is
implementation
a
dual-base
strategy
that
utilizes
an
amine
base
combined
with
soluble
halide
scavenger
allows
use
single
air-stable,
commercially
available
Ni(II)-precatalyst
phosphine
ligand
[(R,S)-Josiphos]
combination
promote
aminations
across
broad
scope
pharmaceutically
relevant
nucleophiles
at
catalyst
loadings
as
low
1.0
mol
%.
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.
A
palladium-catalyzed
Catellani-type
[2+2+2]
annulation
reaction
of
aryl
iodides,
bromothiophenes,
and
norbornadiene,
which
proceeds
via
a
tandem
Heck
coupling/double
C-H
bond
activation
retro-Diels-Alder
pathway
to
access
thiophene-fused
polyaromatics,
is
reported.
The
key
feature
this
protocol
represents
NBD/NBE
retaining
annulation.
Herein,
we
report
a
novel
palladium(II)-initiated
borono-Catellani
reaction
that
utilizes
widely
accessible
aryl
boronic
acids
serve
as
both
the
reaction-initiating
and
-terminating
substrates
for
first
time.
The
was
facilitated
by
cooperative
catalysis
between
Pd(OAc)2
NBE,
with
air
serving
oxidizing
agent,
opening
new
venues
developing
Catellani-type
reactions.
Importantly,
this
method
is
compatible
wide
range
of
substrates,
including
naphthaleneboronic
acid,
phenylboric
acid
derivatives,
alkyl
iodides,
under
these
environmentally
friendly
mild
conditions,
thereby
demonstrating
versatile
functional
group
compatibility
synthesis
valuable
polysubstituted
aromatics.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
While
the
palladium/norbornene
(Pd/NBE)
cooperative
catalysis
has
become
increasingly
useful
for
arene
functionalization,
its
substrate
scope
been
mainly
restricted
to
reactive
aryl
iodides
and
bromides.
Despite
being
a
more
available
attractive
feedstock,
common
chlorides
have
not
used
as
substrates
Pd/NBE
catalysis.
Herein
we
report
first
general
Pd/NBE-catalyzed
vicinal
difunctionalization
of
chlorides.
Enabled
by
combination
secondary-amide-substituted
NBEs
XPhos
ligand,
diverse
can
now
undergo
successful
ortho
alkylation,
amination,
acylation
with
different
ipso
terminations,
including
olefination,
hydrogenation,
alkynylation.
To
show
utility
this
method,
late-stage
derivatizations
complex
bioactive
compounds
sequential
functionalizations
polyhaloarenes
achieved.
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Abstract
While
the
palladium/norbornene
(Pd/NBE)
cooperative
catalysis
has
become
increasingly
useful
for
arene
functionalization,
its
substrate
scope
been
mainly
restricted
to
reactive
aryl
iodides
and
bromides.
Despite
being
a
more
available
attractive
feedstock,
common
chlorides
have
not
used
as
substrates
Pd/NBE
catalysis.
Herein,
we
report
first
general
Pd/NBE‐catalyzed
vicinal
difunctionalization
of
chlorides.
Enabled
by
combination
secondary‐amide‐substituted
NBEs
XPhos
ligand,
diverse
can
now
undergo
successful
ortho
alkylation,
amination,
acylation
with
different
ipso
terminations,
including
olefination,
hydrogenation,
alkynylation.
To
show
utility
this
method,
late‐stage
derivatizations
complex
bioactive
compounds
sequential
functionalizations
polyhaloarenes
achieved.
