Angewandte Chemie,
Год журнала:
2023,
Номер
136(8)
Опубликована: Дек. 20, 2023
Abstract
Multicomponent
reactions,
particularly
those
entailing
four
or
more
reagents,
have
presented
a
longstanding
challenge
due
to
the
inherent
complexities
associated
with
balancing
reactivity,
selectivity,
and
compatibility.
In
this
study,
we
describe
palladium‐catalyzed
multi‐component
fluoroalkylative
carbonylation
of
1,3‐enynes.
A
series
products
featuring
three
active
functional
groups‐allene,
fluoroalkyl,
carboxyl,
were
efficiently
selectively
integrated
in
single
chemical
operation.
Furthermore,
intricate
fluoroalkyl‐substituted
pyrimidinones
can
be
constructed
by
simply
altering
1,3‐bisnucleophilic
reagent.
This
approach
also
provides
valuable
strategy
for
late‐stage
modification
naturally
occurring
molecules
concise
construction
diverse
cyclic
compounds.
ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2144 - 2150
Опубликована: Янв. 25, 2024
The
modular
four-component
carbonylation
of
unsaturated
hydrocarbons
represents
an
elegant
strategy
for
the
one-pot
synthesis
complex
carbonyl
compounds.
However,
this
is
currently
focused
on
1,2-difunctionalization
olefins
or
alkynes,
and
1,4-alkylcarbonylation
1,3-enynes
remains
unexplored.
In
study,
we
report
a
Ni-catalyzed
CF3-containing
under
1
atm
CO,
which
affords
tetra-substituted
CF3-allenyl
ketones
with
good
yields
selectivity.
This
protocol
features
mild
conditions,
broad
substrate
scope,
acceptable
functional
group
compatibility.
Control
experiments
revealed
that
reactivity
oxime
esters
(regulated
by
leaving
groups)
polarity
matching
are
crucial
success
cascade.
Preliminary
mechanistic
studies
suggest
acyl
nickel
key
intermediate
in
transformation.
Science China Chemistry,
Год журнала:
2022,
Номер
66(1), С. 139 - 146
Опубликована: Дек. 12, 2022
Abstract
Fluorinated
heterocycles
play
a
vital
role
in
pharmaceutical
and
agrochemical
industries.
Hence,
rapid
efficient
construction
of
fluorinated
remains
highly
demanded.
Herein,
difluoroalkylative
carbonylative
cyclization
unactivated
alkenes
ethylene
gas
enabled
by
palladium
catalysis
has
been
developed
for
the
first
time
toward
synthesis
α-carbonyl
difluoro-modified
glutarimides.
This
procedure
can
also
be
applied
to
GeMigliptin
which
is
medicine
approved
treatment
type
2
diabetes
mellitus.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(8)
Опубликована: Дек. 20, 2023
Multicomponent
reactions,
particularly
those
entailing
four
or
more
reagents,
have
presented
a
longstanding
challenge
due
to
the
inherent
complexities
associated
with
balancing
reactivity,
selectivity,
and
compatibility.
In
this
study,
we
describe
palladium-catalyzed
multi-component
fluoroalkylative
carbonylation
of
1,3-enynes.
A
series
products
featuring
three
active
functional
groups-allene,
fluoroalkyl,
carboxyl,
were
efficiently
selectively
integrated
in
single
chemical
operation.
Furthermore,
intricate
fluoroalkyl-substituted
pyrimidinones
can
be
constructed
by
simply
altering
1,3-bisnucleophilic
reagent.
This
approach
also
provides
valuable
strategy
for
late-stage
modification
naturally
occurring
molecules
concise
construction
diverse
cyclic
compounds.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(9), С. 990 - 996
Опубликована: Янв. 18, 2024
Comprehensive
Summary
Catalytic
four‐component
radical
carbonylation
of
unactivated
alkenes
has
recently
been
recognized
as
a
robust
protocol
for
rapid
construction
various
structurally
diverse
carbonyl
compounds.
Given
the
significance
fluorine‐containing
groups,
this
reaction
class
extensively
applied
to
assembly
variety
perfluoroalkyl
carboxylic
acid
derivatives
by
transition
metal
catalysis.
Herein,
we
report
visible‐light‐driven
relay
1,2‐perfluoroalkylation
aminocarbonylation
using
CO
gas
source
and
4CzIPN
organic
photocatalyst.
A
wide
range
amines
were
well
tolerated,
providing
valuable
β‐perfluoroalkylated
amides
with
generally
good
yields
high
chemoselectivity.
Organic Letters,
Год журнала:
2024,
Номер
26(22), С. 4779 - 4783
Опубликована: Май 29, 2024
A
new
strategy
to
obtain
β,γ-unsaturated
ketones
via
the
cross-coupling
of
1,3-butadiene,
alkyl
bromides,
and
arylboronic
acids
under
1
bar
CO
with
nickel
as
catalyst
has
been
developed.
This
newly
developed
four-component
carbonylation
procedure
features
advantages
including
using
a
cheap
catalytic
system,
high
step
economy,
mild
reaction
conditions,
excellent
1,4-regioselectivity,
thereby
providing
sustainable
alternative
tool
for
production
compared
present
tactics.
To
elucidate
application
potential
this
method,
olefin
synthons
are
derived
from
representative
coupling
product.
Organic Letters,
Год журнала:
2022,
Номер
24(31), С. 5791 - 5796
Опубликована: Авг. 2, 2022
A
novel
visible-light-mediated
difluoroalkylation
of
1-(allyloxy)-2-(1-arylvinyl)benzenes
and
1-(1-arylvinyl)-2-(vinyloxy)benzenes
for
the
synthesis
bis-difluoroalkylated
benzoxepines
2H-chromenes
is
developed.
This
method
features
mild
reaction
conditions,
good
regioselectivity,
a
wide
substrate
scope,
functional-group
compatibility,
late-stage
modification.
Preliminary
mechanistic
studies
reveal
that
generation
CF2CO2Et
radical
more
prone
to
with
double
bond
aryl
group.
Green Chemistry,
Год журнала:
2023,
Номер
25(10), С. 3989 - 3994
Опубликована: Янв. 1, 2023
A
visible
light-mediated
C
sp
3
–Br
homolysis-initiated
radical
cyclization
cascade
delivering
diverse
3-difluorolactam
substituted
chroman-4-ones
with
excellent
regioselectivity
and
diastereoselectivity.
Colloids and Interface Science Communications,
Год журнала:
2023,
Номер
53, С. 100704 - 100704
Опубликована: Фев. 3, 2023
In
this
paper,
a
novel
nanocomposite
was
prepared
as
heterogeneous
catalyst
using
layered
double
hydroxide
(LDH),
and
copper(II)
nanoparticles
stabilized
on
guanidine
(Mg-Al
[email
protected](II))
(1).
This
used
in
multi-component
reactions
for
the
synthesis
of
2-(1H-tetrazole-5-yl)
acrylonitrile
derivatives
with
high
yield
short
reaction
times.
Identification
nanocatalyst
performed
by
FT-IR,
EDS,
FE-SEM,
TEM,
XRD
TGA
techniques.
showed
thermal
stability,
specific
surface
area,
good
reusability
up
to
4
times
without
significant
loss
activity.
addition,
excellent
activity,
easy
separation,
milder
conditions
are
among
factors
that
make
an
catalytic
system
these
reactions.
under
green
chemistry
various
benzaldehyde
derivatives,
malononitrile,
sodium
azide,
optimal
amount
nanocatalyst.
The
support
LDH
which
have
become
popular
field
catalysts
due
its
very
low
cost
well
combination
structural
features
such
abundant
hydroxyl
groups
surface,
tunability
host
layers,
interlayer
anions,
regular
distribution
metal
cations,
etc.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 5, 2025
ConspectusTransition-metal-catalyzed
carbonylation
coupling
methods
have
been
accepted
as
an
essential
tool
for
producing
carbonylated
products
over
the
past
few
decades.
Despite
its
long-standing
history
and
widespread
industrial
applications,
several
challenges
remain
in
chemistry.
These
include
reliance
on
precious
metal
catalysts,
need
of
high-energy
radiation,
difficulties
unactivated
chemical
bonds,
etc.
As
alternative
to
classic
two-electron
transfer
process,
single-electron-transfer
(SET)-mediated
has
emerged
a
powerful
achieve
elusive
transformations.
Over
years,
commonly
available
functional
handles,
such
alkenes
alkyl
halides,
via
single-electron
pathway
valuable
area
research.Our
team
dedicated
developing
new
reactions
using
bulk
chemicals
construct
high-value
products.
broad
synthetic
motivating
us
explore
SET-mediated
transformations
two
key
classes
chemicals:
alkanes
halides.
Specifically,
our
work
centered
main
approaches:
(1)
Single-electron
reduction
C(sp3)-X
bonds:
this
strategy
leverages
activate
promoting
formation
carbon
radicals,
which
turn
promotes
subsequent
addition
metals
or
CO.
However,
significant
challenge
lies
highly
negative
potential
certain
substrates
[Ered
<
-2
V
compared
saturated
calomel
electrode
(SCE)
iodides].
these
challenges,
intrinsic
reducibility
CO
reactivity
various
carbonyl-metal
intermediates
facilitate
smooth
reaction
progress.
(2)
oxidative
C(sp3)-H
emphasizes
efficiency,
high
atomic
utilization,
minimal
waste
by
bypassing
traditional
preactivation
methods.
Using
3d
we
successfully
performed
aminocarbonylation
alkoxycarbonylation
wide
range
bonds
(such
those
aliphatic
alkanes,
ethers,
amines,
etc.).
The
above
approaches
also
enabled
radical
relay
alkenes,
allowing
precise
control
pathways.
Such
improves
both
efficiency
selectivity.
advancements
transition
photoredox
catalysis
resulting
oxyalkylative
carbonylation,
aminoalkylative
fluoroalkylative
double
rearrangement
carbonylation.SET-mediated
significantly
enhances
sustainability
scalability
process
reducing
catalysts
enabling
milder
conditions.
Additionally,
carefully
controlling
intermediates,
fine-tuned
produce
with
This
flexibility
expands
applications
chemistry
processes.
Finally,
place
particular
emphasis
application
drug
discovery,
where
they
serve
handles
late-stage
modification
bioactive
molecules.
applicability
enriches
toolbox
synthesis,
efficient
functionalization
complex
versatile
approach
accelerate
discovery
novel
therapeutic
agents,
making
it
critical
modern
medicinal
