The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
89(1), P. 656 - 664
Published: Dec. 7, 2023
We
demonstrate
that
oxime
ester
derivatives
can
be
used
as
both
a
halogen
atom
transfer
(XAT)
agent
and
an
imine
source
under
photocatalytic
conditions,
allowing
the
radical
amination
of
alkyl
halides,
resulting
in
formation
broad
scope
imines.
Hydrolysis
latter
gives
direct
access
to
corresponding
primary
amines.
Mechanistically,
reaction
is
believed
proceed
through
aryl
intermediates,
which
are
responsible
for
activation
halides
via
XAT.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 6247 - 6258
Published: April 10, 2024
Aryl-substituted
bicyclo[1.1.1]pentane
(BCP-aryl)
derivatives
represent
the
most
important
bioisosteres
of
biaryl
scaffolds
and
widely
exist
in
numerous
complex
pharmaceutical
molecules.
The
current
synthetic
method
limitations
using
only
tertiary
radical
precursors,
prefunctionalized
heteroarenes,
toxic
transition
metals,
expensive
photocatalysts
make
it
urgent
to
develop
a
more
simple
practical
protocol.
To
confront
enrich
Minisci-type
chemistry,
herein,
we
disclose
photocatalytic
multicomponent
reaction
for
synthesis
various
(halo)alkyl
BCP-aryls
[1.1.1]propellane,
alkyl
halides,
unfunctionalized
heteroarenes
as
starting
materials.
Diverse
kinds
radicals
(primary,
secondary,
carbons)
derived
from
chlorides,
bromides,
fluoroalkyl
iodides
are
very
compatible
this
transformation.
practicability
is
additionally
boosted
by
product
derivatizations
late-stage
functionalization
pharmaceutically
relevant
mechanistic
studies
demonstrate
that
relay
mechanism
initiated
consecutive
photoinduced
electron
transfer
(ConPET)
process
operation.
We
anticipate
methodology
would
act
useful
tool
biaryl-type
drug
derivatives,
ultimately
resulting
great
utility
discovery
program.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(32), P. 17527 - 17550
Published: Aug. 2, 2023
The
C–O
bond
is
ubiquitous
in
biologically
active
molecules,
pharmaceutical
agents,
and
functional
materials,
thereby
making
it
an
important
group.
Consequently,
the
development
of
bond-forming
reactions
using
catalytic
strategies
has
become
increasingly
research
topic
organic
synthesis
because
more
conventional
methods
involving
strong
base
acid
have
many
limitations.
In
contrast
to
ionic-pathway-based
methods,
copper-promoted
radical-mediated
formation
experiencing
a
surge
interest
owing
renaissance
free-radical
chemistry
photoredox
catalysis.
This
Perspective
highlights
appraises
state-of-the-art
techniques
this
burgeoning
field.
contents
are
organized
according
different
reaction
types
working
models.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5278 - 5305
Published: Jan. 1, 2024
This
review
summarizes
the
latest
methodological
advances
in
photocatalytic
C(sp
3
)–H
functionalization,
with
a
particular
emphasis
on
formation
of
C–P,
C–B,
C–S
bonds,
etc
.,
and
some
prominent
efforts
asymmetric
C–H
functionalization.
Chem,
Journal Year:
2024,
Volume and Issue:
10(4), P. 1240 - 1251
Published: Feb. 13, 2024
The
photoactivation
of
sulfonium
salt
EDA
(electron
donor-acceptor)
complexes
provides
a
mild
platform
for
aryl-radical-mediated
halogen
atom
transfer
activation
wide
range
functionalized
alkyl
iodides,
including
tertiary
iodides.
Using
an
aryl
with
carbonate
as
inexpensive
donor
complex
formation,
the
general
reaction
has
been
applied
in
divergent,
metal-free
photochemical
approach
to
nitriles
and
amides.
This
divergency
was
made
possible
by
tuning
isocyanide
radical
traps.
For
example,
identification
readily
accessible,
bench-stable,
crystalline
amide
containing
grants
access
nitrile
products
complete
selectivity.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(50), P. 6340 - 6361
Published: Jan. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(22), P. 15176 - 15185
Published: May 21, 2024
Stepwise
oxidative
addition
of
copper(I)
complexes
to
form
copper(III)
species
via
single
electron
transfer
(SET)
events
has
been
widely
proposed
in
copper
catalysis.
However,
direct
observation
and
detailed
investigation
these
fundamental
steps
remain
elusive
owing
largely
the
typically
slow
rate
instability
species.
We
report
herein
a
novel
aryl-radical-enabled
stepwise
pathway
that
allows
for
formation
well-defined
alkyl–CuIII
from
CuI
complexes.
The
process
is
enabled
by
SET
an
aryl
diazonium
salt
CuII
radical.
Subsequent
iodine
abstraction
alkyl
iodide
radical
affords
radical,
which
then
reacts
with
complex.
structure
resultant
[(bpy)CuIII(CF3)2(alkyl)]
characterized
NMR
spectroscopy
X-ray
crystallography.
Competition
experiments
have
revealed
at
different
iodides
undergo
consistent
carbon-centered
radicals.
intermediate
formed
during
identified
as
four-coordinate
complex,
[CuII(CH3CN)2(CF3)2],
through
electronic
paramagnetic
resonance
(EPR)
studies.
catalytic
relevance
high-valent
organo-CuIII
demonstrated
C–C
bond-forming
reductive
elimination
reactivity.
Finally,
localized
orbital
bonding
analysis
formal
CuIII
indicates
inverted
ligand
fields
σ(Cu–CH2)
bonds.
These
results
demonstrate
catalysis
provide
general
strategy
investigate
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5839 - 5843
Published: July 1, 2024
Light-mediated
Halogen-Atom
Transfer
(XAT)
has
become
a
significant
methodology
in
contemporary
synthesis.
Unlike
α-aminoalkyl
and
silyl
radicals,
ligated
boryl
radicals
(LBRs)
have
not
been
extensively
explored
as
halogen
atom
abstractors.
In
this
study,
we
introduce
NHC-ligated
boranes
optimal
radical
chain
carriers
for
the
intermolecular
reductive
hydroalkylation
hydroarylation
of
electron-deficient
olefins
by
using
direct
UV-A
light
irradiation.
DFT
analysis
allowed
us
to
rationalize
critical
role
NHC
ligand
facilitating
efficient
propagation.
