The
construction
of
chiral
tetrasubstituted
α-fluoro-α-cyano
carbonyl
compounds
remains
a
key
challenge
in
synthetic
organic
chemistry
because
their
popularity
multiple
disciplines.
In
this
paper,
we
report
the
copper-catalyzed
asymmetric
fluorinated
tertiary
radical
cyanation
reaction
cyclic
α-iodo-α-fluoroindanones
with
TMSCN
to
achieve
nitriles
carbon–fluorine
quaternary
stereogenic
centers.
Thus,
an
array
optically
active
monofluoroacyl
were
synthesized
high
efficiency
and
excellent
enantioselectivities
(up
91%
yield,
99%
ee).
Moreover,
mechanistic
investigations,
including
experiments,
conducted
clarify
pathway
stereochemical
outcomes.
A
Ni-catalyzed
protocol
for
the
regioselective
and
stereoselective
three-component
fluoroalkylthiolation
of
alkynes
with
fluoroalkyl
halides
thiosulfonates
is
presented.
This
reductive
difunctionalization
provides
an
efficient
strategy
rapid
construction
fluoroalkyl-incorporated
vinylthioethers
under
mild
conditions
in
moderate
to
good
yields.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
Comprehensive
Summary
Herein,
we
report
a
photo‐induced,
metal‐/additive‐free
protocol
for
the
difluoromethylation
of
N
‐heteroaromatics
with
[bis(difluoroacetoxy)iodo]benzene
as
reagent.
The
affords
difluoromethylated
in
moderate
to
good
yield
(up
91%).
transformation
is
compatible
wide
range
substrates
and
has
tolerance
towards
various
functional
groups.
Moreover,
synthetic
value
this
method
further
demonstrated
by
applications
gram‐scale
synthesis
late‐stage
functionalization
biologically
important
molecules.
The
δ-lactam
motif
is
a
privileged
pharmacophore
in
drug
design
and
development.
While
these
biologically
relevant
molecules
could
be
assembled
through
two-component
cyclization,
modular
approach
to
constructing
structures
via
multicomponent
reaction
with
unactivated
alkenes
as
starting
materials
rare.
Herein,
we
report
tandem
that
integrates
alkene-dialkylation
radical-involved
ring-opening
cyclization
under
single
metal-electron-shuttle
catalysis,
which
represents
the
most
expeditious
access
fluorinated
δ-lactams
from
simple
alkenes.
Vinyl
difluoromethylene
units
(−CF−)
significantly
enhance
the
bioactivity
and
physical
chemical
properties
of
compounds.
Despite
recent
advances
in
introducing
vinyl
units,
radical-mediated
formation
these
motifs
remains
largely
unexplored.
A
novel
serial
catalytic
strategy
for
selective
defluoroalkylation
trifluoromethyl
alkenes
has
been
developed,
utilizing
photocatalytic
defluorocarboxylation
followed
by
photoinduced
iron-catalyzed
decarboxylation/isomerization.
The
reaction
involves
generating
difluoroallyl
radicals,
tautomerizing
to
proceeding
through
radical
addition
alkylation.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 17, 2025
The
advancement
of
robust
synthetic
methodologies
for
generating
fluorinated
quaternary
carbon
chiral
centers
is
highly
sought
after
in
the
fields
organic
and
medicinal
chemistry.
This
study
successfully
provides
such
compounds
through
cobalt-catalyzed
asymmetric
Negishi
coupling
reactions
α-bromo-α-fluoro
ketones
with
aryl/alkenyl
zinc
reagents.
adjustment
unsymmetric
N,N,N-tridentate
(CUT)
ligands
played
a
key
role
improving
reactivity
selectivity
cobalt
catalysis,
preventing
formation
hydrodebromination
byproducts,
accommodating
sterically
hindered
substrates
heterocycles.
Control
kinetic
experiments
reveal
that
transmetalation
serves
as
rate-limiting
step,
mechanistic
characteristic
sets
newly
developed
cross-couplings
apart
from
previous
methodologies.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 24, 2025
Comprehensive
Summary
The
[2+1]
cycloaddition
of
alkynes
with
fluoroalkyl
carbenes
represents
the
most
straightforward
approach
for
constructing
fluoroalkylated
cyclopropenes.
However,
until
now,
this
strategy
has
not
been
applicable
to
difluoromethyl
carbene,
as
its
precursor,
diazomethane,
tends
undergo
[3+2]
form
pyrazoles.
This
study
presents
first
example
copper‐catalyzed
cyclopropenation
employing
difluoroacetaldehyde
triftosylhydrazone
carbene
precursor.
A
wide
range
internal
and
terminal
alkynes,
featuring
diverse
functional
groups,
were
efficiently
converted
into
corresponding
cyclopropenes
in
good
high
yields.
Mechanistic
investigations,
supported
by
DFT
calculations,
revealed
that
bulky
Tp
Br3
Cu(NCMe)
catalyst
plays
a
pivotal
role
facilitating
via
concerted
pathway.
A
novel
Fe-catalyzed
alkylative
aminosulfonylation
of
alkenes
and
alkynes
with
alkyl
halides
O-Ts
activated
hydroxylamines
by
using
Na2S2O4
as
a
reductant
sulfone
source
has
been
developed.
The
metal-electron-shuttle
catalysis
was
discovered
to
be
vital
for
the
highly
efficient
generation
sulfonyl
radicals
anions
without
requiring
organometallic
intermediates.
This
method
provides
access
sulfonamides
from
easily
available
features
broad
substrate
scope.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 28, 2025
Comprehensive
Summary
A
desulfonylative
thiolation
between
heteroaryl
sulfones
and
thiosulfonates
for
the
efficient
synthesis
of
sulfides
was
developed.
The
cross‐electrophile
couplings
proceeded
effectively
via
old
C–SO
2
bond
cleavage
new
C–S
formation
in
presence
cheapest
widely
available
iron
powder
as
mediator
under
transition
metal
catalyst‐free
conditions,
leading
to
a
wide
array
derived
from
benzo[
d
]thiazole,
]oxazole,
thiazole,
1,3,4‐thiadiazole,
1
H
‐tetrazole
modest
excellent
yields.
In
addition,
reaction
exhibited
good
functional
group
compatibility,
protocol
could
also
be
applicable
use
selenosulfonate
substrate
subjected
scale‐up
with
equal
ease.
Notably,
unreacted
readily
recovered
after
by
resorting
attracting
property
magnetic
stir
bar
iron.
