The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(21), С. 15263 - 15275
Опубликована: Окт. 13, 2021
The
multiple
C–H
bonds
of
biaryl
ynones
render
the
6-exo-trig
regioselective
activation
dearomatization
to
spiro[5.5]trienones
challenging
since
competing
reactions
on
Ar1
or
ortho-C–H
Ar3
may
result
in
5-exo-trig
cyclization
indenones
ortho-dearomatization,
respectively.
We
here
report
an
unprecendented
with
aldehydes
via
double
functionalization
where
a
regiospecific
remote
unactivated
para-C–H
efficiently
furnishes
acylated
spiro[5.5]trienones.
This
cascade
features
green
catalyst
and
solvent
high
atom-
step-economy.
Chemical Science,
Год журнала:
2022,
Номер
13(11), С. 3169 - 3175
Опубликована: Янв. 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
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7014 - 7019
Опубликована: Сен. 18, 2023
Organoelectrophotocatalytic
generation
of
acyl
radicals
from
formamides
and
aldehydes
to
synthesize
acylated
3-CF3-2-oxindoles
has
been
developed.
This
protocol
features
a
monocatalytic
system
using
9,10-phenanthrenequinone
(PQ)
both
as
catalyst
hydrogen
atom
transfer
(HAT)
reagent,
which
avoids
the
use
an
external
HAT
metal
oxidant.
A
variety
have
obtained
in
satisfactory
yields
CF3-substituted
N-arylacrylamides
via
tandem
radical
cyclization.
Green Chemistry,
Год журнала:
2024,
Номер
26(12), С. 7331 - 7336
Опубликована: Янв. 1, 2024
A
novel
photocatalytic
acylation
strategy
was
developed
harnessing
tetrabutylammonium
decatungstate
(TBADT)
as
a
hydrogen
atom
transfer
(HAT)
photocatalyst
to
facilitate
the
direct
coupling
of
aldehydes
with
N-heterocycles
at
ambient
temperature.
Organic Letters,
Год журнала:
2025,
Номер
27(10), С. 2526 - 2531
Опубликована: Март 5, 2025
Herein,
we
introduce
an
efficient
and
straightforward
strategy
for
the
selective
C-H
esterification
alkylation
of
quinoxalin-2(1H)-ones
with
aldehydes.
A
key
feature
our
study
is
ability
to
perform
both
using
different
types
The
reaction
system
highly
compatible
a
range
aldehydes,
yielding
C3-esterified
C3-alkylated
products
in
moderate-to-good
yields.
applicability
this
approach
further
enhanced
by
its
scalability
through
continuous-flow
synthesis,
late-stage
modification
significant
molecules,
product
derivatization.
Our
mechanistic
investigations
reveal
radical
relay
mechanism,
triggered
hydrogen
atom
transfer
process.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Дек. 10, 2021
Abstract
While
aldehydes
represent
a
classic
class
of
electrophilic
synthons,
the
corresponding
acyl
radicals
are
inherently
nucleophilic,
which
exhibits
umpolung
reactivity.
Generation
typically
requires
noble
metal
catalysts
or
excess
oxidants
to
be
added.
Herein,
we
report
convenient
and
green
approach
access
radicals,
capitalizing
on
neutral
eosin
Y-enabled
hydrogen
atom
transfer
(HAT)
photocatalysis
with
aldehydes.
The
generated
underwent
SOMOphilic
substitutions
various
functionalized
sulfones
(X–SO
2
R’)
deliver
value-added
products.
merger
Y
sulfone-based
SOMOphiles
provides
versatile
platform
for
wide
array
aldehydic
C–H
functionalizations,
including
fluoromethylthiolation,
arylthiolation,
alkynylation,
alkenylation
azidation.
present
protocol
features
characteristics,
such
as
being
free
metals,
harmful
additives;
step-economic;
redox-neutral;
amenable
scale-up
assisted
by
continuous-flow
technology.
ACS Catalysis,
Год журнала:
2022,
Номер
12(21), С. 13549 - 13554
Опубликована: Окт. 20, 2022
A
dual
photocatalytic
protocol
was
developed
to
generate
acyl
radicals
from
readily
available
aldehydes
via
hydrogen
atom
transfer
(HAT).
Synergistic
cooperation,
being
supported
by
DFT
studies,
between
earth-abundant
iron(III)chloride
and
9,10-diphenylanthracene
(DPA)
activate
the
aldehyde
for
a
HAT
step
proved
be
an
efficient,
economic,
green
route
hydroacylation
of
electron-deficient
alkenes
under
UV-light
irradiation
with
broad
functional
group
compatibility.
This
methodology
can
conveniently
scaled
up
applied
produce
valuable
materials
renewable
feedstock
chemicals.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(44)
Опубликована: Сен. 9, 2022
Oxidative
N-heterocyclic
carbene
(NHC)
organocatalysis,
typically
leading
to
the
formation
of
acyl
azolium
reactive
intermediates,
constitutes
one
most
important
activation
strategies
for
NHC-catalyzed
chemical
transformations.
Here,
we
report
an
unprecedented
oxidative
radical
NHC
catalysis
by
using
peroxyester
as
external
single-electron
oxidant
realize
divergent
difunctionalization
olefins.
The
key
success
this
chemistry
is
catalytic
generation
oxygen
radicals
that
could
trigger
intermolecular
hydrogen
atom
transfer
activate
inert
C-H
bonds,
thereby
enabling
productive
relay
process.
With
protocol,
commonly
used
general
chemicals
serve
precursors
allow
efficient
synthesis
value-added
products
in
a
straightforward
and
cost-effective
manner.
Preliminary
mechanistic
investigations,
including
control
experiments
DFT
calculations,
shed
light
on
organocatalytic
reaction
mechanism.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(9), С. 2522 - 2528
Опубликована: Янв. 1, 2022
A
photocatalytic
protocol
for
the
synthesis
of
β-amino
acid
ester
and
ketone
derivatives
is
developed
using
simple
easy-to-synthesize
oxime
oxalate
phenylglyoxylate
as
difunctionalization
reagents.
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.
