ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3181 - 3190
Published: Feb. 14, 2024
Cross-coupling
reactions
have
been
well
received
as
one
of
the
most
popular
protocols
for
ketone
synthesis.
As
an
important
coupling
partner,
bench-stable
and
commercially
available
alkyl
boronic
acids
are
widely
used
in
transition
metal
catalysis,
but
they
rarely
utilized
radical
precursors
acylative
reactions.
Herein,
we
reported
energy-transfer-enabled
acylation
using
free
via
NHC/photo
dual
catalysis.
This
protocol
could
efficiently
promote
Suzuki-type
cross-coupling
between
acyl
imidazoles
multicomponent
alkylacylations
alkenes,
thus
producing
various
ketones
with
structural
diversity.
Additionally,
products
can
readily
transform
into
a
large
number
structurally
interesting
fine
chemicals.
Preliminary
mechanistic
studies
shed
light
on
unique
reaction
mechanism.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(3), P. 1522 - 1586
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
overview
of
the
recent
applications
organocatalytic
strategies
in
pharmaceutical
synthesis,
with
focus
on
preparation
antiviral,
anticancer,
neuroprotective,
cardiovascular,
antibacterial
and
antiparasitic
agents.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 11984 - 11999
Published: Sept. 19, 2022
Radical/radical
cross-coupling
reactions
represent
an
efficient
and
straightforward
approach
for
the
construction
of
chemical
bonds
accordingly
have
drawn
increasing
attention
over
past
decades.
In
order
to
achieve
synthetically
useful
transformations,
a
persistent
radical
should
be
coupled
with
transient
in
accordance
effect
(PRE).
However,
known
radicals
outnumber
by
far
types
free
radicals,
which
limits
widespread
application
PRE,
until
today.
Thus,
development
between
has
been
focus,
meanwhile
transition-metal
catalysis
successfully
implemented
artificially
prolong
lifetimes,
allowing
their
utilization
formal
radical/radical
cross-couplings.
Complementary
research
field
recently
uncovered
that
organocatalytically
generated
NHC-derived
ketyl
are
type
catalytically
radicals.
NHC-catalyzed
transformations
aldehydes
carboxylic
acid
derivatives
enabled
disclosure
ever-increasing
number
interesting
reactions,
different
from
traditional
ionic
processes,
offering
otherwise
inaccessible
activation
modes.
These
discoveries
opened
door
NHC
organocatalysis
manipulation
reactions.
Due
its
obvious
potential
synthetic
organic
chemistry,
it
is
timely
provide
perspective
on
this
emerging
field.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7072 - 7079
Published: March 22, 2022
The
2,3-dihydrobenzofuran
scaffold
is
widely
found
in
natural
products
and
biologically
active
compounds.
Herein,
dearomatizing
2,3-fluoroaroylation
of
benzofurans
with
aroyl
fluorides
as
bifunctional
reagents
to
access
2,3-difunctionalized
dihydrobenzofurans
reported.
reaction
that
occurs
by
cooperative
NHC/photoredox
catalysis
provides
3-aroyl-2-fluoro-2,3-dihydrobenzofurans
moderate
good
yield
high
diastereoselectivity.
Cascades
proceed
via
radical/radical
cross-coupling
a
benzofuran
radical
cation
generated
the
photoredox
cycle
neutral
ketyl
formed
through
NHC
cycle.
redox-neutral
transformation
exhibits
broad
substrate
scope
functional
group
compatibility.
With
anhydrides
reagents,
aroyloxyacylation
achieved
strategy
can
also
be
applied
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(29), P. 8491 - 8506
Published: Jan. 1, 2022
Allenes
are
valuable
organic
molecules
that
feature
unique
physical
and
chemical
properties.
They
not
only
often
found
in
natural
products,
but
also
act
as
versatile
building
blocks
for
the
access
of
complex
molecular
targets,
such
pharmaceuticals,
functional
materials.
Therefore,
many
remarkable
elegant
methodologies
have
been
established
synthesis
allenes.
Recently,
more
methods
radical
allenes
developed,
clearly
emphasizing
associated
great
synthetic
values.
In
this
perspective,
we
will
discuss
recent
important
advances
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(11), P. 3169 - 3175
Published: Jan. 1, 2022
The
modulation
of
selectivity
highly
reactive
carbon
radical
cross-coupling
for
the
construction
C-C
bonds
represents
a
challenging
task
in
organic
chemistry.
N-Heterocyclic
carbene
(NHC)
catalyzed
transformations
have
opened
new
avenue
acyl
With
this
method,
selective
an
with
alkyl
efficient
was
successfully
realized.
However,
reaction
radicals
vinyl
has
been
much
less
investigated.
We
herein
describe
NHC
and
visible
light-mediated
photoredox
co-catalyzed
1,4-sulfonylacylation
1,3-enynes,
providing
structurally
diversified
valuable
tetrasubstituted
allenyl
ketones.
Mechanistic
studies
indicated
that
ketyl
are
formed
from
aroyl
fluorides
via
oxidative
quenching
photocatalyst
excited
state,
generated
chemo-specific
sulfonyl
addition
to
finally,
key
provides
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(46), P. 13367 - 13383
Published: Jan. 1, 2023
This
review
summarizes
recent
advances
in
combining
photo-
and
N-heterocyclic
carbene
catalysis,
as
well
provides
an
outlook
on
future
opportunities
challenges.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 8270 - 8293
Published: May 13, 2024
As
one
of
the
most
important
key
intermediates,
NHC-bound
acylazolium-based
ionic
transformations
have
been
intensively
explored
in
past
two
decades.
With
expeditious
development
NHC-catalyzed
radical
recent
years,
acylazolium
chemistry
has
reached
another
level,
with
number
relevant
publications
increasing
significantly.
However,
a
summary
focused
on
acylations
NHC-derived
acyl
azoliums
classified
according
to
mechanistic
difference
not
reported.
Such
detailed
classification
and
deep
analysis
provide
opportunities
for
better
understanding
history
trend
this
field.
In
review,
reactions
N-heterocyclic
carbene
(NHC)-derived
are
systematically
introduced.
The
achievements
challenges
within
area
also
summarized
discussed
at
end.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(33), P. 17925 - 17931
Published: June 7, 2021
Single-electron
N-heterocyclic
carbene
(NHC)
catalysis
has
gained
attention
recently
for
the
synthesis
of
C-C
bonds.
Guided
by
density
functional
theory
and
mechanistic
analyses,
we
report
light-driven
aliphatic
α-amino
ketones
using
single-electron
NHC
operators.
Computational
experimental
results
reveal
that
reactivity
key
radical
intermediate
is
substrate-dependent
can
be
modulated
through
steric
electronic
parameters
NHC.
Catalyst
potential
harnessed
in
visible-light
driven
generation
an
acyl
azolium
species
undergoes
selective
coupling
with
various
partners
to
afford
diverse
ketone
products.
This
methodology
showcased
direct
late-stage
functionalization
amino
acids
pharmaceutical
compounds,
highlighting
utility
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
56(99), P. 15484 - 15495
Published: Jan. 1, 2020
Recent
advances
are
presented
in
NHC
catalysis
employing
aliphatic
aldehydes
as
substrates
for
the
generation
of
various
carbene-bound
intermediates
and
subsequent
interception
with
electrophiles/nucleophiles.
