Handbook of CH‐Functionalization,
Год журнала:
2022,
Номер
unknown, С. 1 - 28
Опубликована: Окт. 2, 2022
Abstract
The
article
provides
a
summary
of
the
recent
developments
in
using
carboxylic
acids
and
derivatives
as
aryl,
alkenyl,
alkyl
electrophiles
for
CH
functionalization.
This
manifold
exploits
ubiquitous
after
oxidative
addition
decarbonylation
absence
external
oxidants
under
Rh,
Pd,
Ni,
Ir
catalysis.
Mechanistically,
acyl
RC(O)X
bond
to
low
valent
metals
is
followed
by
decarbonylation,
resulting
net
generation
R[M]
broad
range
functionalization
processes.
covers
aroyl
chlorides,
fluorides,
anhydrides,
acids,
esters
amides,
other
related
derivatives.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(44), С. 18617 - 18625
Опубликована: Окт. 28, 2021
This
Article
describes
the
development
of
a
decarbonylative
Pd-catalyzed
aryl–fluoroalkyl
bond-forming
reaction
that
couples
fluoroalkylcarboxylic
acid-derived
electrophiles
[RFC(O)X]
with
aryl
organometallics
(Ar–M′).
was
optimized
by
interrogating
individual
steps
catalytic
cycle
(oxidative
addition,
carbonyl
de-insertion,
transmetalation,
and
reductive
elimination)
to
identify
compatible
pair
coupling
partners
an
appropriate
Pd
catalyst.
These
stoichiometric
organometallic
studies
revealed
several
critical
elements
for
design.
First,
uncatalyzed
background
reactions
between
RFC(O)X
Ar–M′
can
be
avoided
using
M′
=
boronate
ester.
Second,
de-insertion
Ar–RF
elimination
are
two
slowest
when
RF
CF3.
Both
dramatically
accelerated
upon
changing
CHF2.
Computational
reveal
favorable
F2C–H---X
interaction
contributes
accelerating
in
this
system.
Finally,
transmetalation
is
slow
X
difluoroacetate
but
fast
F.
Ultimately,
these
enabled
(SPhos)Pd-catalyzed
difluoromethylation
neopentylglycol
esters
difluoroacetyl
fluoride.
Synthesis,
Год журнала:
2022,
Номер
54(17), С. 3667 - 3697
Опубликована: Май 6, 2022
Abstract
Numerous
studies
on
the
activation
of
carbon–fluorine
bonds
have
been
reported
in
recent
years.
For
example,
acyl
fluorides
utilized
as
versatile
reagents
for
acylation,
arylation,
and
even
fluorination.
In
this
review,
we
focus
compounds
with
bonds,
highlight
advances
strategies
their
C–F
via
transition-metal
catalysis,
N-heterocyclic
carbene
(NHCs)
organophosphine
classical
nucleophilic
substitution
reactions.
1
Introduction
2
Transition-Metal-Mediated
Bond
Activation
2.1
Acylation
(Carbonyl-Retentive)
Coupling
Reactions
2.2
Decarbonylative
2.3
by
Other
Transition
Metals
3
N-Heterocyclic
Carbenes
3.1
NHC-Catalyzed
Cycloaddition
Acyl
Fluorides
3.2
Radical
Functionalization
3.3
Nucleophilic
Fluorination
(Hetero)aromatics
4
Phosphines
4.1
Phosphine-Catalyzed
Direct
4.2
Indirect
5
Classical
Substitution
6
Miscellaneous
Examples
7
Summary
Perspective
Catalysts,
Год журнала:
2025,
Номер
15(2), С. 191 - 191
Опубликована: Фев. 19, 2025
In
this
study,
we
developed
a
palladium-catalyzed
decarbonylative
nucleophilic
halogenation
reaction
using
inexpensive
and
readily
available
acid
anhydrides
as
substrates.
This
approach
effectively
circumvents
the
instability
of
acyl
chlorides
low
reactivity
fluorides.
The
Pd/Xantphos
catalyst
system
exhibited
excellent
compatibility
with
thermodynamically
kinetically
challenging
reductive
elimination
C–X
bonds
(X
=
I,
Br,
Cl)
from
Pd(II)
intermediates.
Notably,
for
electron-donating
substrates,
adopting
an
open
significantly
improved
efficiency.
positive
effect
may
be
due
to
reversible
nature
CO
insertion
deinsertion,
which
helps
direct
toward
desired
pathway
by
allowing
generated
exit
system.
Mechanistic
studies
suggest
that
proceeds
through
highly
reactive
halide
intermediate,
followed
unimolecular
fragment
coupling
(UFC)
via
decarbonylation
or
alternative
involving
formation
activated
anionic
palladate
complex
in
presence
lithium
halide.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(20), С. 4091 - 4095
Опубликована: Янв. 1, 2022
A
novel
Ni-catalysed
deamidative
fluorination
of
twist
amides
with
electrophilic
fluorinating
reagents
is
reported,
affording
diverse
acyl
fluorides
in
good
yields.
Results in Chemistry,
Год журнала:
2023,
Номер
6, С. 101130 - 101130
Опубликована: Сен. 20, 2023
Transition
metals
are
well
known
for
their
catalytic
behaviours
the
activation
of
Carbon-Carbon
(C-C)
bond.
Many
chemists
have
created
various
important
developments
in
this
field
during
last
decades.
In
present
review,
only
a
few
instances
C-C
bond
using
transition
metal
catalyst
and
mechanism
been
disclosed,
which
is
useful
information
creating
new
ways
to
break
these
bonds.
This
review
includes
recent
advances
cyclic,
saturated
unsaturated
carbon–carbon
bonds
utilizing
as
number
different
systems.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 11905 - 11917
Опубликована: Июль 25, 2024
Aryl
halides
are
widely
recognized
as
crucial
and
versatile
feedstocks
for
organic
synthesis.
However,
in
palladium-catalyzed
reactions,
while
oxidative
addition
of
carbon–halogen
bonds
is
thermodynamically
favorable,
the
reverse
reaction─reductive
elimination
with
formation
bonds─poses
a
significant
challenge.
As
part
conducting
series
decarbonylative
transformations
acyl
halides,
we
developed
nucleophilic
halogenation
fluorides
chlorides
through
Pd-mediated
reductive
C–X
bond.
These
reactions
enable
synthesis
aryl
iodides,
bromides,
using
alkali
metal
halides.
Regarding
reaction
mechanism,
Xantphos
ligand
emerges
factor
promoting
elimination,
leading
to
stable
Pd(0)
intermediate
an
adduct
trans-(Xantphos)Pd(ArCO)X.
Two
proposed
mechanisms
involve
Xantphos-promoted
outer-sphere
substitution
direct
transhalogenation
between
In
latter
or
react
form
corresponding
iodides
bromides
situ
under
mild
conditions
decarbonylation,
yielding
desired
via
unimolecular
fragment
coupling.
Importantly,
it
evident
that
controlling
rate
halide
appropriate
combination
substrates
success
this
reaction.
Indeed,
found
gradual
iodide
pivotal
managing
undesired
generation
I2,
known
catalyst
poison.
This
observation
enables
us
fine-tune
conditions,
thereby
improving
selectivity
transformation.
result,
achieve
enhanced
yields
final
products
establish
more
sustainable
robust
catalytic
processes.
advancement
not
only
boosts
applicability
reliability
our
synthetic
methodology
but
also
underscores
potential
broader
adoption
Organometallics,
Год журнала:
2022,
Номер
41(12), С. 1509 - 1518
Опубликована: Июнь 6, 2022
The
formation
of
benzoyl(benzoato)palladium
complexes
via
a
stoichiometric
reaction
between
benzoyl
fluorides,
Pd(OAc)2,
hydrosilane
and
phosphine
is
reported.
NMR
studies
the
acyl
palladium
complex
reveal
generation
mechanism
indicate
that
intermediate
in
palladium-catalyzed
reduction
fluorides
using
hydrosilane.
Furthermore,
acyl(carboxylato)palladium
provides
an
fluoride
derived
from
through
with
another
fluoride.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(29)
Опубликована: Март 10, 2023
Carboxylic
acids
are
abundant,
low
cost
and
environmentally
friendly,
direct
convert
carboxylic
into
valued-added
compounds
in
high
demand.
Herein,
we
report
a
Rh(I)
catalyzed
decarbonylative
borylation
of
aryl
alkyl
acid
using
TFFH
as
activator.
This
protocol
features
excellent
functional-group
tolerance
broad
substrate
scope
including
natural
product
drugs.
A
gram-scale
reaction
Probenecid
is
also
presented.
In
addition,
the
utility
this
strategy
highlighted
by
one-pot
borylation/
derivatization
sequence.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(8)
Опубликована: Май 17, 2023
Abstract
Transition‐metal‐catalyzed
directed
C−H
functionalization
reactions
are
a
powerful
method
to
construct
N
‐heterocycles.
However,
compared
the
formation
of
five‐
and
six‐membered
rings,
that
seven‐membered
rings
has
been
much
less
explored.
Here,
synthesis
benzo[
c
]azepine‐1,3(2
H
)‐diones
is
described,
which
benzene‐fused
imides,
from
hydroxamates
α,β‐unsaturated
acyl
fluorides
via
activation
using
Cp*Rh(III)
catalyst.
Under
mild
reaction
conditions,
this
affords
bear
substituent
at
5‐position.
