ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 17642 - 17653
Published: Nov. 15, 2024
The
combination
of
N-heterocyclic
carbene
(NHC)
organocatalysis
with
photochemical
activation
is
becoming
increasingly
established
as
an
approach
for
conducting
radical
organic
reactions
under
mild
and
practical
conditions.
As
comparatively
easy
to
prepare
handle
compounds,
alkyl
silanes
are
attractive
substrates
chemistry
desilylative
mesolysis
the
corresponding
cations
known
be
rapid.
Here,
we
report
successful
application
benzyl
silane
derivatives
source
radicals
in
dual
NHC/photoredox-catalyzed
radical–radical
coupling
acyl
fluorides.
Relatively
electron-rich
reacted
smoothly
afford
ketones
generally
good
yields,
while
optimization
NHC
photocatalyst
allowed
a
wider
scope
including
primary
substrates.
Furthermore,
initial
experiments
revealed
that
organosilanes
bearing
N-,
O-
S-heteroatoms
can
also
serve
sources
these
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(32), P. 6915 - 6920
Published: Aug. 8, 2024
Ketones,
as
essential
functional
group
skeletons,
have
garnered
significant
interest
due
to
their
diverse
transformations.
Herein,
we
describe
a
versatile
photoredox
catalyzed
deacylation-aroylation
strategy
that
enables
the
direct
transformation
of
alkyl
ketones
aryl
ketones.
This
process
involves
deacylation
dihydroquinazolinones
derived
from
generate
radicals,
followed
by
subsequent
NHC-catalyzed
or
NHC-mediated
radical
aroylation.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
Herein,
we
report
a
formal
C–C
bond
azidation
and
cyanation
of
unactivated
aliphatic
ketones
using
commercially
available
tosyl
azide
cyanide,
respectively.
A
visible-light-mediated
organophotocatalyst
enables
radical
ketone-derived
pro-aromatic
dihydroquinazolinones
(under
mostly
redox-neutral
conditions)
as
supported
by
preliminary
mechanistic
studies.
These
metal-free
scalable
protocols
can
be
used
to
synthesize
tertiary,
secondary,
primary
alkyl
azides
nitriles
with
good
functional
group
tolerance
postsynthetic
diversification
the
group,
including
bioconjugation.
Abstract
Imidazolium‐dithiocarboxylate
zwitterions
(NHC
⋅
CS
2
),
a
novel
organocatalyst
that
derived
from
N‐heterocyclic
carbene
(NHC),
was
used
to
activate
cyclopropenones.
Under
the
catalysis
of
10
mol%
NHC
2,
range
phenols,
alcohols,
primary
and
secondary
amines
react
with
cyclopropenones
produce
trisubstituted
α
,
β
‐unsaturated
esters
amides
in
46–95%
yield.
More
than
68
products,
including
7
natural
product
derivatives
have
been
synthesized
through
this
method.
Mechanism
study
showed
act
as
Lewis
base
C=C
double
bond
trigger
ring‐opening
reaction.
HRMS
analysis
indicated
formation
key
adduct
cyclopropenone.
importantly,
demonstrated
completely
different
catalytic
activity
catalysts,
latter
one
cannot
catalyse
these
reactions.
Advanced Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
Abstract
Isoflavonoids
represent
a
privileged
scaffold
among
various
bioactive
natural
products,
rendering
their
structural
diversification
through
green
synthesis
and
subsequent
biological
evaluations
compelling
research
area.
In
this
study,
an
NHC
organocatalytic
radical
acylalkylation
of
1,3‐enynes
using
salicylaldehydes
is
presented,
followed
by
cascade
intramolecular
annulation,
yielding
series
fluorinated
isoflavone
derivatives
with
substantial
yields
under
environmental‐friendly
conditions.
This
approach,
distinguished
its
excellent
modularity
high
functional
group
tolerance,
represents
unprecedented
1,3,4‐trifunctionalization
designed
for
the
isoflavones
in
single
step.
Furthermore,
it
demonstrated
that
these
synthesized
isoflavonoids
effectively
suppress
proliferation
breast
cancer
cells,
most
potent
compound
8
also
inhibiting
migration
MDA‐MB‐231
cells.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
A
class
of
prearomatic
carboxylic
acid
p-quinol
ester
radical
precursors
has
been
developed
successfully,
which
could
undergo
homolytic
cleavage
the
para
C-O
bond
esters
via
pyridine-boryl
radical-induced
aromatization
in
presence
pyridines
and
diboron
reagents,
affording
corresponding
alkyl
decarboxylation
from
carboxyl
situ.
In
addition,
were
further
applied
substitution
with
phenylsulfonyl
compounds
self-coulpings.
This
method
not
only
provides
a
new
approach
to
generation
intermediate
but
also
expands
application
boron
radicals.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 21, 2025
A
metal-free,
visible-light-induced
NHC-catalyzed
multiple-component
reaction
involving
aldehydes
and
aryl
thianthrenium
salts
for
the
carboacylation
of
alkenes
is
reported.
In
this
reaction,
NHC-activated
afforded
Breslow
intermediates,
which
reduced
generated
radicals.
The
resulting
radicals
underwent
radical
addition
reactions
to
yield
arylacylation
products,
in
presence
iodoalkane,
participated
halogen
atom
transfer
process
generate
alkyl
facilitate
olefin
alkylacylation.
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
We
report
an
organophotocatalyst-enabled
oxidant-free
C–S/C–Se
bond
coupling
of
(un)symmetrical
1,2-diketones
via
pro-aromatic
dihydroquinazolinones/benzothiazolines,
employing
readily
accessible
disulfides/diselenides.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(8), P. 1711 - 1711
Published: April 11, 2025
Traditionally
employed
as
hydrogenation
reagents,
benzothiazolines
have
emerged
versatile
carbanion
and
radical
transfer
playing
a
vital
role
in
the
construction
of
various
carbon–carbon
bonds.
The
cutting-edge
progress
photochemistry
chemistry
prompted
study
visible
light-driven
reactions,
bringing
into
vibrant
focus.
Their
chemical
processes
been
uncovered
to
encompass
variety
activation
mechanisms,
with
five
distinct
modes
having
identified.
This
work
reviews
innovative
applications
donors
alkyl
or
acyl
groups,
achieving
hydroalkylation
hydroacylation
substitution.
By
examining
their
diverse
this
review
highlights
potential
serving
groups
for
further
research
development.
Moreover,
will
offer
exemplary
inspiration
synthetic
chemists,
contributing
ongoing
evolution
utility
organic
synthesis.
