Herein
we
present
photoinduced
cobaloxime-catalyzed
selective
remote
desaturation
of
aliphatic
alcohols.
This
transformation,
which
proceeds
efficiently
at
room
temperature,
facilitates
the
synthesis
valuable
cyclic
and
acyclic
allylic
homoallylic
alcohols
from
readily
available
saturated
Remarkably,
this
method
obviates
need
for
external
oxidants,
noble
metal
catalysts,
phosphine
ligands.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4665 - 4680
Опубликована: Март 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Chemical Science,
Год журнала:
2023,
Номер
14(13), С. 3580 - 3586
Опубликована: Янв. 1, 2023
Herein,
a
photo-induced
palladium
catalyzed
aryl-to-alkyl
radical
relay
Heck
reaction
at
α-C(sp
3
)–H
site
of
amide
has
been
developed.
This
method
is
scalable
and
operationally
simple.
Mechanistic
studies
reveal
the
nature
this
transformation.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 22, 2024
Abstract
Drawing
inspiration
from
nature
has
long
been
a
cornerstone
of
chemical
innovation,
with
natural
systems
offering
wealth
untapped
potential
for
discovery.
In
this
minireview,
we
delve
into
the
burgeoning
field
cobaloxime
catalysis
in
organic
synthesis,
which
mimics
catalytic
activity
organometallic
alkylcobalamine
enzymes.
Our
focus
lies
on
elucidating
latest
advancements
area,
as
well
delineating
primary
mechanistic
pathways
at
play.
By
describing,
and
comparing
these
mechanisms,
provide
comprehensive
overview
current
state‐of‐the‐art,
while
also
shedding
light
key
unresolved
challenges
that
await
further
exploration.
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8666 - 8675
Опубликована: Май 20, 2024
Catalytic
dehydrogenative
borylation
of
alkenes
is
arguably
the
most
straightforward
approach
for
synthesizing
alkenyl
boronates,
as
it
eliminates
need
alkene
or
boranes
prefunctionalizion.
While
transition-metal
catalysis
has
conventionally
been
employed
this
transformation,
competitive
side
reactions
including
hydroborylation,
overborylation,
and
regioisomer
formation
always
exist.
In
study,
we
present
a
radical
catalytic
borylation,
which
involves
synergistic
merger
photoredox/HAT/cobalt
catalysis,
thereby
circumventing
necessity
noble
metals,
sacrificial
hydrogen
acceptors,
high
temperatures.
This
method
employs
stable
cost-effective
amine
borane
reagents
feedstocks,
resulting
in
sole
byproduct
H2.
methodology
facilitates
conversion
diverse
array
functionalized
into
valuable
organoboron
reagents.
Furthermore,
late-stage
complex
molecules
demonstrates
levels
site
selectivity.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(17), С. 4394 - 4399
Опубликована: Янв. 1, 2023
Herein,
we
report
an
effective
C–H
bond
activation-alkylation
strategy
for
2-iodobenzoyl
protected
cyclic
amines
at
the
N
-α-position
through
a
visible-light
mediated
1,5-hydrogen
atom
transfer
(HAT)
process.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(7), С. 4985 - 4992
Опубликована: Фев. 6, 2024
Unsaturated
amides
represent
common
functional
groups
found
in
natural
products
and
bioactive
molecules
serve
as
versatile
synthetic
building
blocks.
Here,
we
report
an
iron(II)/cobalt(II)
dual
catalytic
system
for
the
syntheses
of
distally
unsaturated
amide
derivatives.
The
transformation
proceeds
through
iron
nitrenoid-mediated
1,5-hydrogen
atom
transfer
(1,5-HAT)
mechanism.
Subsequently,
radical
intermediate
undergoes
hydrogen
abstraction
from
vicinal
methylene
by
a
cobaloxime
catalyst,
efficiently
yielding
β,γ-
or
γ,δ-unsaturated
derivatives
under
mild
conditions.
efficiency
Co-mediated
HAT
can
be
tuned
varying
different
auxiliaries,
highlighting
generality
this
protocol.
Remarkably,
desaturation
protocol
is
also
amenable
to
practical
scalability,
enabling
synthesis
carbamates
ureas,
which
readily
converted
into
various
valuable
molecules.
Organic Letters,
Год журнала:
2024,
Номер
26(13), С. 2662 - 2667
Опубликована: Март 26, 2024
A
novel
class
of
alkyne-tethered
amides
facilitates
an
unprecedented
photoinduced
palladium-catalyzed
radical
relay
formal
[5
+
2]
reaction.
This
innovative
strategy
allows
for
the
rapid
construction
diverse
fused
benzoazepine
structures,
yielding
structurally
and
compelling
compounds.
With
a
broad
substrate
scope
excellent
functional
group
tolerance,
methodology
synthesizes
biologically
active
Notably,
resulting
tricyclic
benzo[b]azepines
offer
diversification
opportunities
through
simple
transformations.
DFT
calculations
elucidate
seven-membered
ring
closure
mechanism
involving
alkenyl
Pd(I)
rebound
alongside
concerted
metalation–deprotonation
(CMD)
process.
SynOpen,
Год журнала:
2022,
Номер
06(04), С. 286 - 305
Опубликована: Авг. 24, 2022
Abstract
C–H
bond
functionalization
is
one
of
the
most
effective
strategies
for
rapid
synthesis
cyclic
amines
containing
substituents
on
ring,
which
are
core
structures
many
bioactive
molecules.
However,
it
much
more
challenging
to
perform
this
strategy
remote
bonds
compared
α-C–H
amines.
This
graphical
review
aims
provide
a
concise
overview
transition-metal-catalyzed
methods
Examples
categorized
and
demonstrated
according
mechanistic
pathways
that
initiate
reactions
amine
substrates.
Where
relevant,
selected
substrate
scope
detailed
reaction
mechanisms
given.