Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(70)
Опубликована: Сен. 21, 2024
Abstract
The
synthesis
of
α‐tertiary
amino
acids
(ATAAs),
which
are
pivotal
components
in
natural
metabolism
and
pharmaceutical
innovation,
continues
to
attract
significant
research
interest.
Despite
substantial
advancements,
the
pursuit
a
facile,
versatile,
resource‐efficient
methodology
remains
an
area
active
development.
In
this
work,
we
introduce
visible
light‐triggered
three‐component
reaction
involving
readily
available
nitrosoarenes,
N
‐acyl
pyrazoles,
allyl
or
(bromomethyl)benzenes
under
mild
conditions.
This
approach
enables
straightforward
assembly
wide
array
ATAA
derivatives
(42
examples)
commendably
high
yields
(up
89
%).
Mechanistic
investigations
elucidate
that
proceeds
through
dehydration
condensation
between
nitrosoarenes
pyrazoles
generate
ketimine
intermediates.
is
followed
by
light‐driven
halogen
atom
transfer
(XAT)
process
radical
addition,
culminating
formation
desired
products.
showcases
excellent
functional
group
compatibility
late‐stage
derivatization
potential,
offering
new
insights
avenues
for
analogs.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(7), С. 4422 - 4433
Опубликована: Март 17, 2023
The
development
of
excited-state
palladium-catalyzed
alkylative
cyclization
acrylamides
and
the
alkylation
quinoxalinones
is
described.
application
a
variety
primary,
secondary,
tertiary
unactivated
alkyl
halides
as
radical
precursors
use
simple
catalyst
system
are
highlights
this
reactivity
manifold.
reactions
exhibit
wide
scope,
occur
under
mild
conditions,
furnish
products
in
excellent
yields.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(48)
Опубликована: Авг. 10, 2024
Abstract
Our
study
unveils
a
pioneering
methodology
that
effectively
distributes
Pd
species
within
zeolitic
imidazolate
framework‐8
(ZIF‐8).
We
demonstrate
can
be
encapsulated
ZIF‐8
as
atomically
dispersed
function
an
excited‐state
transition
metal
catalyst
for
promoting
carbon–carbon
(C−C)
cross‐couplings
at
room
temperature
using
visible
light
the
driving
force.
Furthermore,
same
material
reduced
250
°C,
forming
nanoparticles
in
ZIF‐8.
This
shows
high
rates
and
selectivity
carbon
dioxide
hydrogenation
to
methanol
under
industrially
relevant
conditions
(250
50
bar):
7.46
mol
−1
h
>99
%.
results
correlations
of
structure
with
performances
experimental
theoretical
levels.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 24, 2025
Pd-catalyzed
photochemical
reductive
alkylation
of
quinoxalin-2(1H)-ones
and
dibenzoxazepines
with
readily
available
alkyl
bromides
has
been
developed.
The
dependence
oxidative
chemoselectivity
on
the
nature
base
was
established.
A
variety
primary,
secondary,
tertiary
halides
have
successfully
employed
in
this
transformation,
which
features
a
wide
substrate
scope
under
mild
reaction
conditions
is
also
applicable
to
dibenzoxazepines.
We
unveil
a
novel
strategy
that
leverages
cost-effective
fluorine-containing
sources
for
rapid
synthesis
of
fluorinated
com-pounds
through
multicomponent
reactions.
Our
study
introduces
visible
light-driven
palladium-catalyzed
1,4-difluoromethyl
difunctionalization
conjugated
dienes,
capitalizing
on
the
abundant
industrial
resource
chlorodifluoro-methane
(ClCF2H,
Freon-22).
Illuminated
by
blue
LED
light,
palladium
catalyst
orchestrates
efficient
single
electron
reduction
Freon-22's
C-Cl
bond,
yielding
CF2H
radicals.
This
versatile
protocol
accommodates
an
extensive
array
amines,
sulfinates,
and
enolates
as
nucleophiles,
delivering
regioselective
products
via
SN2'
substitution
allylic
intermediate.
Redox-neutral
in
nature,
this
transformation
finds
utility
late-stage
functionalization
drug
molecules,
while
broad
compatibility
with
diverse
functional
groups
dienes
underscores
its
versa-tility.
Initial
insights
suggest
involvement
difluoromethyl
radical
intermediate,
unveiling
direct
mild
avenue
to
harness
radicals
from
Freon-22.
The Chemical Record,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
Abstract
Azomethines
is
a
class
of
compounds,
which
have
traditionally
served
as
electrophilic
substrates,
but
their
reactions
with
radicals
long
been
limited.
Photocatalysis
provided
ample
opportunities
for
promoting
these
reactions,
wide
variety
reagents
serving
precursors
radicals.
Besides
regular
addition
mode
at
the
azomethine
fragment,
oxidative
pathway,
in
C=N
bond
remains
product,
has
become
possible
by
proper
selection
redox
catalyst.
This
review
summarizes
new
developments
this
rapidly
developing
field
over
past
five
years.
New
concepts
on
activation
towards
radical
attack
are
discussed.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(23)
Опубликована: Апрель 4, 2024
Abstract
A
new
cross‐coupling
of
trifluoromethyl
arenes
has
been
realized
via
multiphoton
photoredox
catalysis.
Trifluoromethyl
were
demonstrated
to
undergo
selective
mono‐defluorinative
alkylation
under
mild
reaction
conditions
providing
access
a
series
valuable
α,α‐difluorobenzylic
compounds.
The
shows
broad
substrate
scope
and
general
functional
group
tolerance.
In
addition
the
electron‐deficient
that
are
easily
reduced
corresponding
radical
anion,
more
challenging
electron‐rich
substrates
also
successfully
applied.
Steady‐State
Stern‐Volmer
quenching
studies
indicated
by
excited
Ir‐based
photocatalyst.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5719 - 5724
Опубликована: Июнь 28, 2024
A
novel
photocatalytic
palladium-induced
6-endo-selective
alkyl
Heck
reaction
of
unactivated
iodides
and
bromides
has
been
described.
This
strategy
facilitates
the
gentle
efficient
synthesis
a
variety
5-phenyl-1,2,3,6-tetrahydropyridine
derivatives.
It
demonstrates
broad
substrate
tolerance
excellent
6-endo
selectivity.
Unlike
high-temperature
requirements
traditional
reactions,
this
transformation
efficiently
proceeds
at
room
temperature
shows
significant
promise
for
industrial-scale
applications.
Mechanistic
investigations
reveal
that
via
hybrid
palladium–radical
process.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(32)
Опубликована: Июнь 27, 2023
Abstract
Mannich‐type
reactions
involving
alkylzinc
reagents
have
been
developed
using
different
strategies.
We
show
that
the
addition
of
these
organometallic
species
to
sulfonyl
imines
occurs
upon
simple
heating
and
affords
Mannich
products
in
moderate
excellent
yields
(14
examples,
30–99
%).
Interestingly,
N
‐alkyl
were
also
found
be
suitable
partners
after
activation
as
an
acyliminium
by
acetyl
chloride
(12
49–86
%)
or,
more
originally,
TMSCl
26–87
These
methods
proved
complementary,
leading
preparation
both
‐protected
secondary
or
tertiary
amines
N‐unprotected
good
yields,
with
increased
eco‐compatibility,
under
conditions.
