Organic Letters,
Год журнала:
2023,
Номер
25(18), С. 3325 - 3329
Опубликована: Апрель 27, 2023
Herein,
an
NHC
(N-heterocyclic
carbene)-catalyzed
radical
coupling
reaction
between
aldehydes
and
azobis(isobutyronitrile)
(AIBN)
has
been
developed.
This
method
provides
efficient
convenient
approach
for
the
synthesis
of
β-ketonitriles
containing
a
quaternary
carbon
center
(31
examples,
up
to
>99%
yield)
utilizing
commercially
available
substrates.
protocol
features
broad
substrate
scope,
good
functional
group
tolerance,
high
efficiency
under
metal-free
mild
conditions.
ACS Catalysis,
Год журнала:
2022,
Номер
12(19), С. 11984 - 11999
Опубликована: Сен. 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.
Chemical Science,
Год журнала:
2022,
Номер
13(29), С. 8491 - 8506
Опубликована: Янв. 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,
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 Chemistry Frontiers,
Год журнала:
2024,
Номер
11(7), С. 2112 - 2133
Опубликована: Янв. 1, 2024
Organofluorine
compounds
are
of
high
value.
NHC-catalyzed
fluorination
and
fluoroalkylation
have
served
as
powerful
versatile
vehicles
for
accessing
the
related
organofluorines.
This
review
focuses
on
recent
developments
in
this
area.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(8), С. 5229 - 5241
Опубликована: Март 29, 2022
An
N-heterocyclic
carbene
organocatalytic
1,4-difunctionalization
of
1,3-enynes
was
developed.
This
strategy
suitable
for
a
broad
spectrum
substrates
to
efficiently
synthesize
allenic
ketones
bearing
diverse
substituents.
Preliminary
mechanistic
studies
suggest
radical
reaction
pathway
this
acylalkylation
process.
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.
Molecules,
Год журнала:
2023,
Номер
28(7), С. 3027 - 3027
Опубликована: Март 28, 2023
Radical
transformations
are
powerful
in
organic
synthesis
for
the
construction
of
molecular
scaffolds
and
introduction
functional
groups.
In
radical
difunctionalization
reactions,
radicals
first
functionalized
intermediates
can
be
relocated
through
resonance,
hydrogen
atom
or
group
transfer,
ring
opening.
The
resulting
undertake
following
paths
second
functionalization:
(1)
couple
with
other
groups,
(2)
oxidize
to
cations
then
react
nucleophiles,
(3)
reduce
anions
electrophiles,
(4)
metal-complexes.
rearrangements
provide
opportunity
1,3-,
1,4-,
1,5-,
1,6-,
1,7-difunctionalization
products.
Multiple
ways
initiate
reaction
coupling
intermediate
make
reactions
good
at
remote
positions.
These
offer
advantages
synthetic
efficiency,
operation
simplicity,
product
diversity.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 2142 - 2148
Опубликована: Янв. 25, 2023
Allenol
has
been
identified
as
a
versatile
building
block
for
organic
synthesis,
and
numerous
efforts
have
made
to
synthesize
apply
allenol.
However,
limited
obtain
trifluoromethyl-substituted
Here,
by
using
readily
available
1,3-enyne
the
starting
material,
copper-catalyzed
trifluoromethylbenzoxylation
process
was
developed
efficient
synthesis
of
allenols
Togni-II
reagent
reaction
partner.
Triple
roles
reagent,
including
source
trifluoromethyl
group,
hydroxyl
oxidant,
were
elucidated
in
this
transformation.
Moreover,
late-stage
diversification
performed,
which
revealed
application
potential
preparation
various
compounds.
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.
