Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: July 8, 2023
Direct
synthesis
of
ketones
from
aldehydes
features
high
atom-
and
step-economy.
Yet,
the
coupling
with
unactivated
alkyl
C(sp3)-H
remains
challenging.
Herein,
we
develop
via
functionalization
under
photoredox
cooperative
NHC/Pd
catalysis.
The
two-component
reaction
iodomethylsilyl
ether
gave
a
variety
β-,
γ-
δ-silyloxylketones
1,n-HAT
(n
=
5,
6,
7)
silylmethyl
radicals
to
generate
secondary
or
tertiary
following
ketyl
NHC
three-component
addition
styrenes
corresponding
ε-hydroxylketones
generation
benzylic
by
radicals.
This
work
demonstrates
radical
catalysis,
provides
two
three
component
reactions
for
functionalization.
synthetic
potential
this
protocol
was
also
further
illustrated
late-stage
natural
products.
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.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 21, 2024
Abstract
Transition-metal
catalyzed
allylic
substitution
reactions
of
alkenes
are
among
the
most
efficient
methods
for
synthesizing
diene
compounds,
driven
by
inherent
preference
an
inner-sphere
mechanism.
Here,
we
present
a
demonstration
outer-sphere
mechanism
in
Rh-catalyzed
reaction
simple
using
gem
-difluorinated
cyclopropanes
as
allyl
surrogates.
This
unconventional
offers
opportunity
fluorine
recycling
via
C
−
F
bond
cleavage/reformation,
ultimately
delivering
carbofluorination
products.
The
developed
method
tolerates
wide
range
alkenes,
providing
access
to
secondary,
tertiary
fluorides
and
-difluorides
with
100%
atom
economy.
DFT
calculations
reveal
that
formation
goes
through
unusual
nucleophilic
allyl-Rh
species
instead
migration
insertion,
generated
carbon
cation
then
forms
tetrafluoroborate
fluoride
shuttle.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(3), P. 565 - 568
Published: Jan. 13, 2023
Acyl
fluorides
are
versatile
reagents
in
organic
synthesis.
However,
there
is
no
precedent
to
employ
acyl
as
radical
precursors.
We
herein
report
an
N-heterocyclic
nitrenium
iodide
salt-catalyzed
photoreduction
of
produce
radicals,
which
could
react
with
2-isocyanobiaryls
afford
various
carbonyl
phenanthridines.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: July 8, 2023
Direct
synthesis
of
ketones
from
aldehydes
features
high
atom-
and
step-economy.
Yet,
the
coupling
with
unactivated
alkyl
C(sp3)-H
remains
challenging.
Herein,
we
develop
via
functionalization
under
photoredox
cooperative
NHC/Pd
catalysis.
The
two-component
reaction
iodomethylsilyl
ether
gave
a
variety
β-,
γ-
δ-silyloxylketones
1,n-HAT
(n
=
5,
6,
7)
silylmethyl
radicals
to
generate
secondary
or
tertiary
following
ketyl
NHC
three-component
addition
styrenes
corresponding
ε-hydroxylketones
generation
benzylic
by
radicals.
This
work
demonstrates
radical
catalysis,
provides
two
three
component
reactions
for
functionalization.
synthetic
potential
this
protocol
was
also
further
illustrated
late-stage
natural
products.
