Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Cooperative
NHC/photoredox
catalyzed
deconstruction–reconstruction
of
aryl
cyclopropanes
was
described
to
access
various
α-acylated
cyclopropane
derivatives.
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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 19, 2025
Radical-radical
cross-coupling
(RCC)
offers
a
promising
approach
for
carbon-carbon
bond
formation
in
organic
synthesis,
particularly
creating
complex,
three-dimensional
molecules.
However,
achieving
both
cross-
and
enantioselectivity
RCC
reactions
has
remained
significant
challenge.
Here,
we
report
novel
metallaphotoredox
platform
that
enables
highly
enantioselective
decarboxylative
coupling
of
carboxylic
acid
derivatives
with
aldehydes.
Our
strategy
leverages
independent
control
over
radical
generation
subsequent
through
fine-tuning
common
photocatalyst
simple
chiral
bis(oxazoline)
nickel
catalyst.
This
redox-neutral
protocol
requires
no
exogenous
oxidants
or
reductants
demonstrates
broad
substrate
scope
functional
group
compatibility
the
synthesis
enantioenriched
α-aryl
α-amino
ketones.
The
ketone
products
can
be
readily
transformed
into
valuable
β-amino
alcohols,
streamlining
access
to
these
important
motifs.
Furthermore,
showcase
potential
this
more
challenging
C(sp3)-C(sp3)
alkyl-alkyl
reactions.
unified
alkyl-acyl
represents
advance
asymmetric
catalysis
underscores
exploit
new
mechanisms
solve
long-standing
synthetic
problems.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 19909 - 19918
Опубликована: Июнь 12, 2024
The
catalytic
cross-coupling
of
identical
or
similar
functional
groups
is
a
cornerstone
strategy
for
carbon-carbon
bond
formation,
as
exemplified
by
renowned
methods,
such
olefin
cross-metathesis,
Kolbe
electrolysis,
and
various
cross-electrophile
couplings.
However,
methodologies
coupling
aldehydes─fundamental
building
blocks
in
organic
synthesis─remain
underdeveloped.
While
the
benzoin-type
condensation,
first
reported
1832,
offers
reliable
route
aldehyde
dimerization,
chemo-
enantioselective
nonidentical
yet
aldehydes
remains
an
unsolved
challenge.
Herein,
we
report
unified
platform
enabling
highly
aldehydes.
By
leveraging
nickel
photoredox
catalysis
tandem
with
discrete
activation
strategies
each
aldehyde,
this
mechanistically
distinct
approach
facilitates
union
aldehyde-derived
α-oxy
radical
acyl
radical,
photocatalytically
generated
from
aldehyde.
This
novel
enables
modular
access
to
enantioenriched
α-oxygenated
ketones
two
minimally
differentiated
aliphatic
substituents,
feat
not
achievable
existing
chemocatalytic
biocatalytic
techniques.
synthetic
utility
method
demonstrated
its
application
streamlined
asymmetric
synthesis
medicinally
relevant
molecules.
Additionally,
mechanistic
investigations
rationalize
versatility
exploit
new
pathways
addressing
long-standing
challenges.
The
transformation
of
organoboron
compounds
plays
an
important
role
in
synthetic
chemistry,
and
recent
advancements
boron-migration
reactions
have
garnered
considerable
attention.
Here,
we
report
unprecedented
1,2-boron
migrative
acylation
upon
photocatalysis-facilitated
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3089 - 3099
Опубликована: Янв. 1, 2024
NHC
and
photocatalysis
dual-catalyzed
mono/difluoromethylative
acylation
of
1,3-enynes
was
realized,
providing
fluormethyl-substituted
allenyl
ketones.
SO
2
might
play
a
critical
role
in
achieving
high
reactivity
selectivity.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 16, 2024
The
carboamination
of
unsaturated
molecules
using
bifunctional
reagents
is
considered
an
attractive
approach
for
the
synthesis
nitrogen-containing
compounds.
However,
C-N
have
never
been
employed
in
cyclopropane.
In
this
study,
we
use
N-heterocyclic
carbene
(NHC),
N-benzoyl
saccharin,
as
a
reagent
and
photoredox
catalyst
dual-catalyzed
1,3-aminoacylation
NHCs
play
multiple
roles,
functioning
Lewis
base
catalysts
to
activate
bonds,
promoting
oxidative
quenching
process
PC*,
acting
efficient
acyl
radical
transfer
formation
C-C
bonds.
between
excited-state
PC*
NHC
adduct
key
photooxidation
generality
aryl
cyclopropanes.
Molecules,
Год журнала:
2024,
Номер
29(4), С. 790 - 790
Опубликована: Фев. 8, 2024
Monofluoromethyl
(CH2F)
motifs
exhibit
unique
bioactivities
and
are
considered
privileged
units
in
drug
discovery.
The
radical
monofluoromethylative
difunctionalization
of
alkenes
stands
out
as
an
appealing
approach
to
access
CH2F-containing
compounds.
However,
this
strategy
remains
largely
underdeveloped,
particularly
under
metal-free
conditions.
In
study,
we
report
on
visible
light-mediated
three-component
monofluoromethylation/acylation
styrene
derivatives
employing
NHC
organic
photocatalyst
dual
catalysis.
A
diverse
array
α-aryl-β-monofluoromethyl
ketones
was
successfully
synthesized
with
excellent
functional
group
tolerance
selectivity.
mild
CH2F
generation
from
NaSO2CFH2
holds
potential
for
further
applications
fluoroalkyl
chemistry.
