Herein,
we
report
an
unprecedented
dual
photoexcited
palladium
and
photoredox-catalyzed
remote
C(sp3)-H
acylation
of
amides
free
external
acylating
reagents
through
sequential
N-O/C-H/C-O
bond
cleavage
chemoselective
C-C
formation.
This
catalytic
system
shows
high
efficiency,
good
atom
economy
by
deletion
oxygen,
diverse
functional
group
tolerance.
Experimental
investigation
the
reaction
mechanism
revealed
that
O-acyl
hydroxamides
enabled
generated
alkyl
radicals
via
a
1,5-HAT
process
mediated
amidyl
carboxylate
complex,
which,
undergoing
phosphoranyl
radical-mediated
C-O
cleavage,
leads
to
coupling
with
deliver
final
products.
Chemical Science,
Год журнала:
2023,
Номер
14(46), С. 13367 - 13383
Опубликована: Янв. 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,
Год журнала:
2024,
Номер
14(11), С. 8270 - 8293
Опубликована: Май 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.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(18), С. 4488 - 4515
Опубликована: Янв. 1, 2023
This
review
highlights
the
recent
advances
in
radical
acylated
difunctionalization
of
unsaturated
carbon–carbon
bonds
and
focuses
on
mechanistic
insights
these
transformations.
Chemical Science,
Год журнала:
2024,
Номер
15(12), С. 4564 - 4570
Опубликована: Янв. 1, 2024
We
present
NHC-catalyzed
atroposelective
esterification
of
prochiral
dialdehydes,
delivering
enantioenriched
axially
chiral
diaryl
ethers.
Matched
kinetic
resolutions
amplify
the
enantioselectivity
by
removing
minor
enantiomers
via
over-functionalization.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3181 - 3190
Опубликована: Фев. 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.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(23), С. 3253 - 3260
Опубликована: Июль 20, 2023
Comprehensive
Summary
Secondary
alcohols
bearing
both
axial
and
central
chirality
comprise
attractive
biological
activity
exhibit
excellent
chiral
induction
in
asymmetric
reactions.
However,
only
very
limited
catalytic
approaches
were
developed
for
their
synthesis.
We
herein
describe
visible
light‐mediated
cobalt‐catalyzed
reductive
Grignard‐type
addition
of
aryl
iodides
with
axially
prochiral
biaryl
dialdehydes
leading
to
the
direct
construction
secondary
alcohols.
Preliminary
mechanistic
studies
indicate
that
efficient
kinetic
recognition
diastereomers
might
occur
improve
stereoselectivity,
which
open
a
new
avenue
challenging
cascade
multiple
elements.
This
protocol
features
enantio‐
diastereoselectivity,
green
mild
conditions,
simple
operation,
broad
substrate
scope,
providing
modular
platform
synthesis
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(23), С. 3419 - 3432
Опубликована: Июль 27, 2023
Comprehensive
Summary
Transition
metal‐catalyzed
carbonylation
reactions
represent
a
direct
and
atom‐economical
approach
to
synthesize
carbonyl
compounds
or
their
derivatives
by
using
CO
as
cheap
readily
available
C1
feedstock.
While
of
C(sp
2
)‐hybridized
electrophiles
(
e.g
.,
aryl
halides)
is
well
developed,
less
reactive
unactivated
alkyl
remains
challenging.
Recently,
the
use
earth‐abundant
base
metals
including
Cu,
Co,
Mn,
Fe,
Ni
catalysts
has
enabled
advances
in
carbonylative
coupling
for
approaching
diverse
derivatives,
notably,
some
which
are
synthetic
importance
but
difficult
be
synthesized
through
previous
reported
methods.
Herein,
we
have
summarized
discussed
these
recent
achievements
base‐metal‐catalyzed
C—C,
C—N,
C—O,
C—X
other
source.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(49)
Опубликована: Окт. 18, 2022
Herein,
we
developed
a
new
procedure
on
1,2-dicarbonylative
cyclization
of
4-aryl-1-butenes
with
alkyl
bromides.
Using
simple
copper
catalyst,
two
molecules
carbon
monoxide
were
introduced
into
the
double
bond
formation
four
C-C
bonds
and
ring.
Various
α-tetralones
2,3-dihydroquinolin-4-ones
formed
in
moderate
to
good
yields.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(4), С. 1047 - 1055
Опубликована: Янв. 1, 2023
Visible
light-mediated
NHC
and
photoredox
co-catalyzed
radical
1,2-sulfonylacylation
of
allenes
via
cross-coupling
between
an
allyl
NHC-stabilized
acyl
radical.
