Cell Reports Physical Science,
Год журнала:
2022,
Номер
3(3), С. 100776 - 100776
Опубликована: Фев. 16, 2022
The
formation
of
thermodynamically
accessible
metallacycle
is
crucial
to
achieve
site-selective
C–H
bond
activation.
Here,
we
report
an
isocyanide-bridging
activation
through
the
a
five-membered
palladacycle.
As
such,
proximal
in
aldehyde
moiety
activated
selectively.
subsequent
palladium
shift
and
intramolecular
C=N
insertion
construct
valuable
isoindolinone
framework.
Compared
with
conventional
isocyanide-promoted
activation,
both
carbon
nitrogen
atoms
isocyanide
are
engaged
new
formations.
Notably,
three
types
isoindolinones
can
be
obtained
selectively
by
variations
reaction
conditions.
Mechanistic
studies
shed
light
on
pathways.
Moreover,
synthetic
potential
current
methodology
demonstrated
providing
concise
routes
key
intermediates
indoprofen,
indobufen,
aristolactams,
lennoxamine,
falipamil.
Chemistry - An Asian Journal,
Год журнала:
2022,
Номер
17(15)
Опубликована: Июнь 6, 2022
Abstract
Transition‐metal‐catalyzed
tandem
reactions
have
become
a
mainstay
in
organic
chemistry
owing
to
their
high
atom‐
and
step‐economies.
Metal‐migration‐based
allow
the
engagement
of
simple
starting
materials
for
incorporating
functional
groups
into
certain
positions
constructing
complex
scaffolds,
which
provide
novel
means
that
are
complementary
traditional
cross‐coupling
or
C−H
activation
processes.
In
light
broad
utility
1,4‐Pd
migration
reaction,
this
paper
reviews
its
progress
past
two
decades,
summarizing
process
classifying
it
based
on
insertion,
elimination,
transmetalation,
bond
activation.
Special
emphasis
is
placed
driving
force
Pd
different
mechanisms.
Moreover,
review
also
attempts
summarize
common
strategies
improving
regio‐
site‐selectivities
process.
Organic Letters,
Год журнала:
2023,
Номер
25(13), С. 2190 - 2195
Опубликована: Март 26, 2023
A
palladium-catalyzed
[3
+
2]
annulation
of
substituted
aromatic
amides
with
maleimides
providing
tricyclic
heterocyclic
molecules
in
good
to
moderate
yields
through
weak
carbonyl
chelation
is
reported.
The
reaction
proceeds
via
a
dual
C-H
bond
activation
where
the
first
takes
place
selectively
at
benzylic
position
followed
by
second
meta
afford
five-membered
cyclic
ring.
An
external
ligand
Ac-Gly-OH
has
been
used
succeed
this
protocol.
plausible
mechanism
proposed
for
reaction.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(20), С. 7868 - 7875
Опубликована: Май 11, 2021
The
first
synthesis
of
highly
strained
spirocyclobutane-pyrrolines
via
a
palladium-catalyzed
tandem
Narasaka-Heck/C(sp3
or
sp2)-H
activation
reaction
is
reported
here.
key
step
in
this
transformation
the
δ-C-H
bond
an
situ
generated
σ-alkyl-Pd(II)
species
to
form
five-membered
spiro-palladacycle
intermediate.
concerted
metalation-deprotonation
(CMD)
process,
rate-determining
step,
and
energy
barrier
entire
were
explored
by
density
functional
theory
(DFT)
calculations.
Moreover,
series
control
experiments
was
conducted
probe
reversibility
C(sp3)-H
step.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(17)
Опубликована: Фев. 10, 2022
Abstract
In
the
past
years,
Pd
0
‐catalyzed
C(sp
3
)−H
activation
provided
efficient
and
step‐economical
methods
to
synthesize
carbo‐
heterocycles
via
direct
2
)−C(sp
)
bond
formation.
We
report
herein
that
a
1,4‐Pd
shift
allows
access
N‐heterocycles
which
are
difficult
build
reaction.
It
is
shown
o
‐bromo‐
N
‐methylanilines
undergo
at
‐methyl
group,
followed
by
intramolecular
trapping
or
another
nitrogen
substituent
remote
C−C
formation
generate
biologically
relevant
isoindolines
β‐lactams.
The
product
selectivity
influenced
employed
ligand,
with
NHCs
favoring
of
coupling
against
products
arising
from
N‐demethylation.
Chemical Communications,
Год журнала:
2022,
Номер
58(16), С. 2612 - 2633
Опубликована: Янв. 1, 2022
Advancements
in
the
palladium-catalyzed
functionalization
of
diastereotopic
or
prochiral
C(sp
3
)–H
bonds
generating
stereogenic
centers
and
stereo-arrays
aliphatic
compounds
have
been
highlighted.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(12), С. 4524 - 4530
Опубликована: Март 22, 2021
A
methyl
group
can
have
a
profound
impact
on
the
pharmacological
properties
of
organic
molecules.
Hence,
developing
methylation
methods
and
methylating
reagents
is
essential
in
medicinal
chemistry.
We
report
palladium-catalyzed
dimethylation
reaction
ortho-substituted
iodoarenes
using
dimethyl
carbonate
as
source.
In
presence
K2CO3
base,
are
dimethylated
at
ipso-
meta-positions
iodo
group,
which
represents
novel
strategy
for
meta-C–H
methylation.
With
KOAc
subsequent
oxidative
C(sp3)–H/C(sp3)–H
coupling
occurs;
this
case,
overall
transformation
achieves
triple
C–H
activation
to
form
three
new
C–C
bonds.
These
reactions
allow
expedient
access
2,6-dimethylated
phenols,
2,3-dihydrobenzofurans,
indanes,
ubiquitous
structural
motifs
synthetic
intermediates
biologically
pharmacologically
active
compounds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(18)
Опубликована: Фев. 21, 2023
"Through
space"
palladium/hydrogen
shift
is
an
efficient
strategy
to
achieve
selective
functionalization
of
a
specific
remote
C-H
bond.
Compared
with
relatively
extensive
exploited
1,4-palladium
migration
process,
the
relevant
1,5-Pd/H
was
far
less
investigated.
We
herein
report
novel
pattern
between
vinyl
and
acyl
group.
Through
pattern,
rapid
access
5-membered-dihydrobenzofuran
indoline
derivatives
has
been
achieved.
Further
studies
have
unveiled
unprecedented
trifunctionalization
(vinylation,
alkynylation
amination)
phenyl
ring
through
1,5-palladium
relayed
decarbonylative
Catellani
type
reaction.
A
series
mechanistic
investigations
DFT
calculations
provided
insights
into
reaction
pathway.
Notably,
it
that
in
our
case
prefers
stepwise
mechanism
involving
PdIV
intermediate.
