Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(42)
Published: Aug. 29, 2023
Abstract
The
involvement
of
manganese
radical
for
halogen
atom
transfer
(XAT)
reactions
has
been
esteemed
as
one
reliable
method
but
encountered
with
limited
catalytic
models.
In
this
paper,
a
novel
bimetallic
relay
catalysis
Mn
2
(CO)
10
and
cobaloxime
developed
divergent
dehydrogenative
difluoroalkylation
alkenes
using
commercially
available
difluoroalkyl
bromides.
A
wide
range
structurally
diverse
terminal,
cyclic
internal
well
tetrasubstituted
are
found
to
be
good
coupling
partners
deliver
difluoroalkylated
allylic
products
difluoromethylated
products,
accompanied
the
production
H
by‐product.
This
strategy
features
broad
substrate
scope,
mild
reaction
conditions
excellent
functional
group
compatibility.
Its
success
represents
an
important
step‐forward
expedite
construction
rich
library
products.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 13, 2024
Hypervalent
iodine(III)
compounds
have
found
wide
application
in
modern
organic
chemistry
as
environmentally
friendly
reagents
and
catalysts.
iodine
are
commonly
used
synthetically
important
halogenations,
oxidations,
aminations,
heterocyclizations,
various
oxidative
functionalizations
of
substrates.
Iodonium
salts
arylating
reagents,
while
iodonium
ylides
imides
excellent
carbene
nitrene
precursors.
Various
derivatives
benziodoxoles,
such
azidobenziodoxoles,
trifluoromethylbenziodoxoles,
alkynylbenziodoxoles,
alkenylbenziodoxoles
group
transfer
the
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Development
hypervalent
catalytic
systems
discovery
highly
enantioselective
reactions
chiral
represent
a
particularly
recent
achievement
field
chemistry.
Chemical
transformations
promoted
by
many
cases
unique
cannot
be
performed
any
other
common,
non-iodine-based
reagent.
This
review
covers
literature
published
mainly
last
7-8
years,
between
2016
2024.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3509 - 3524
Published: Feb. 16, 2024
A
photocatalytic
annulation
cascade
of
unactivated
N-alkene-linked
indoles
with
Langlois'
reagent
by
a
radical
relay
is
developed
at
room
temperature
under
blue
LED
irradiation.
The
reaction
afforded
series
tri/difluoromethylated
pyrrolo[1,2-a]indoles
in
moderate
to
good
yields.
DFT
study
suggests
that
the
ascribed
rhodamine
6G-induced
cyclization
involving
vinyl
addition-radical
and
hydrogen-atom-abstraction
(HAA)
processes,
interestingly,
are
applied
as
fluorescent
dyes
into
fluorescence
spectrum
live-cell
imaging.
This
paper
represents
an
initial
example
on
cascades
HAA
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Aug. 29, 2023
The
involvement
of
manganese
radical
for
halogen
atom
transfer
(XAT)
reactions
has
been
esteemed
as
one
reliable
method
but
encountered
with
limited
catalytic
models.
In
this
paper,
a
novel
bimetallic
relay
catalysis
Mn2
(CO)10
and
cobaloxime
developed
divergent
dehydrogenative
difluoroalkylation
alkenes
using
commercially
available
difluoroalkyl
bromides.
A
wide
range
structurally
diverse
terminal,
cyclic
internal
well
tetrasubstituted
are
found
to
be
good
coupling
partners
deliver
difluoroalkylated
allylic
products
difluoromethylated
products,
accompanied
the
production
H2
by-product.
This
strategy
features
broad
substrate
scope,
mild
reaction
conditions
excellent
functional
group
compatibility.
Its
success
represents
an
important
step-forward
expedite
construction
rich
library
products.
ACS Omega,
Journal Year:
2024,
Volume and Issue:
9(26), P. 28129 - 28143
Published: June 19, 2024
An
efficient
and
mild
protocol
for
the
visible
light-induced
radical
cascade
difluoromethylation/cyclization
of
imidazoles
with
unactivated
alkenes
using
easily
accessible
bench-stable
difluoromethyltriphenylphosphonium
bromide
as
precursor
-CF
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(33), P. 6200 - 6205
Published: Aug. 14, 2023
Herein,
we
demonstrate
the
synthesis
and
characterization
of
bench
stable
tri/difluoromethylating
reagents
their
potential
applications
in
redox
neutral
hydro
tri/difluoromethylation
alkenes
enabled
by
visible
light.
The
new
are
obtained
on
a
gram-scale
through
simply
cyclocondensation
commercially
available
anthranilamide
with
phenyltrifluoro
or
difluoromethyl
ketone.
Preliminary
mechanistic
studies
indicated
that
canonical
photoredox
catalytic
cycle
is
being
operative.
DFT
support
this
further
reveal
deprotonation
occurs
before
radical
cleavage.
also
show
better
yield
HCF2
reagent
attributed
to
favorable
expulsion
corresponding
moiety.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(31)
Published: June 5, 2024
Abstract
During
the
past
decade,
radical
difluoromethylation
has
emerged
as
a
powerful
and
versatile
tool
for
incorporation
of
difluoromethyl
into
various
organic
compounds.
These
reactions
feature
mild
reaction
conditions,
very
good
functional
group
compatibilities,
quite
broad
substrate
scopes,
thus
having
drawn
much
attention
got
rapid
developments.
A
diverse
range
precursors
have
been
developed
series
reactions.
This
review
summarizes
discusses
advance
in
reactions,
which
are
organized
according
to
protocols
generating
radical.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(17), P. 3023 - 3028
Published: April 27, 2023
Copper-catalyzed
asymmetric
radical
cyanation
reactions
have
emerged
as
a
powerful
strategy
for
rapid
construction
of
α-chiral
nitriles.
However,
the
directly
decarboxylative
common
alkyl
carboxylic
acids
remain
largely
elusive.
Herein,
we
report
protocol
copper-catalyzed
direct
and
enantioselective
benzylic
acids.
The
in
situ
activation
acid
substrates
by
commercially
inexpensive
hypervalent
iodine(III)
reagent
promoted
yield
radicals
under
mild
reaction
conditions
without
prefunctionalization.
structurally
diverse
chiral
nitriles
were
produced
good
yields
with
high
enantioselectivities.
In
addition,
products
can
be
readily
converted
to
other
useful
compounds
via
further
transformations.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(18), P. 13457 - 13471
Published: Sept. 3, 2024
Organic
molecules
containing
a
difluoroalkyl
group
are
valuable
and
versatile
chemicals
because
of
their
unique
physicochemical
biological
properties.
Accordingly,
the
development
efficient
practical
difluoroalkylation
for
preparation
these
compounds
is
important
attractive.
Herein,
we
demonstrate
photoredox-catalyzed
base-dependent
selective
carbodifluoroalkylation
halodifluoroalkylation
alkenes
using
readily
available
2-(allyloxy)arylaldehydes
[or
2-(allylamino)arylaldehydes]
XCF
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(45), P. 8127 - 8132
Published: Nov. 3, 2023
We
report
herein
a
highly
efficient
copper-catalyzed
protocol
for
the
transformation
of
haloalkynes
to
corresponding
difluoromethylated
alkynes.
This
scalable
exhibits
broad
substrate
scope
and
excellent
functional
group
tolerance,
enabling
late-stage
difluoromethylation
bioactive
molecules.
Additionally,
strategy
utilizing
difluoromethylalkynes
in
gram-scale
reactions
multiple
transformations
has
proven
be
valuable
synthetic
chemistry.
