Organic Letters,
Год журнала:
2021,
Номер
23(6), С. 2314 - 2319
Опубликована: Март 4, 2021
A
highly
regioselective
copper-catalyzed
1,4-chloro-
and
bromotrifluoromethylation
of
1,3-enynes
has
been
presented
for
the
first
time,
which
affords
an
efficient
transformation
to
access
halo-
CF3-containing
tetrasubstituted
allene
derivatives
with
good
excellent
yield.
This
protocol
is
practical
convenient,
in
a
wide
range
functional
groups
are
compatible.
Applications
this
method
gram-scale
preparation
late-stage
functionalization
biologically
active
molecules
also
demonstrated.
Chemical Reviews,
Год журнала:
2018,
Номер
119(4), С. 2192 - 2452
Опубликована: Ноя. 27, 2018
C–H
activation
has
surfaced
as
an
increasingly
powerful
tool
for
molecular
sciences,
with
notable
applications
to
material
crop
protection,
drug
discovery,
and
pharmaceutical
industries,
among
others.
Despite
major
advances,
the
vast
majority
of
these
functionalizations
required
precious
4d
or
5d
transition
metal
catalysts.
Given
cost-effective
sustainable
nature
earth-abundant
first
row
metals,
development
less
toxic,
inexpensive
3d
catalysts
gained
considerable
recent
momentum
a
significantly
more
environmentally-benign
economically-attractive
alternative.
Herein,
we
provide
comprehensive
overview
on
until
summer
2018.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Science,
Год журнала:
2024,
Номер
383(6684), С. 750 - 756
Опубликована: Фев. 15, 2024
Water
can
accelerate
a
variety
of
organic
reactions
far
beyond
the
rates
observed
in
classical
solvents.
However,
using
pure
water
as
solvent
introduces
solubility
constraints
that
have
limited
applicability
efficient
photochemistry
particular.
We
report
here
formation
aggregates
between
pairs
arenes,
heteroarenes,
enamines,
or
esters
with
different
electron
affinities
an
aqueous
medium,
leading
to
oil-water
phase
boundary
through
substrate
melting
point
depression.
The
active
hydrogen
atoms
reactants
engage
bonds
water,
thereby
accelerating
photochemical
reactions.
This
methodology
realizes
appealingly
simple
conditions
for
coupling
complex
solid
molecules,
including
drug
molecules
are
poorly
soluble
water.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Янв. 29, 2024
Abstract
We
highlight
key
contributions
in
the
field
of
direct
radical
C
Ar
−
H
(hetero)aromatic
functionalization
involving
fluorinated
radicals.
A
compilation
Functional
Group
Transfer
Reagents
and
their
diverse
activation
mechanisms
leading
to
release
radicals
are
discussed.
The
substrate
scope
for
each
is
analyzed
classified
into
three
categories
according
electronic
properties
substrates.
Density
functional
theory
computational
analysis
provides
insights
chemical
reactivity
several
through
electrophilicity
nucleophilicity
parameters.
Theoretical
reduction
potentials
also
highlights
remarkable
correlation
between
oxidizing
ability.
It
established
that
highly
(e.g.
⋅OCF
3
)
capable
engaging
single‐electron
transfer
(SET)
processes
rather
than
addition,
which
good
agreement
with
experimental
literature
data.
scale,
based
on
barrier
addition
these
benzene
elaborated
using
high
accuracy
DLPNO‐(U)CCSD(T)
method.
Organic Letters,
Год журнала:
2019,
Номер
21(8), С. 2654 - 2657
Опубликована: Март 29, 2019
A
first
example
of
low-energy
blue-light-mediated
formal
Doyle–Kirmse
reaction
for
gem-difluoroallylation
aryl
diazoesters
has
been
developed.
variety
highly
functionalized
gem-difluoroallyl
containing
esters
bearing
transformable
sulfur
and
bromine
groups
were
efficiently
assembled
with
broad
substrate
scope
under
mild,
catalyst-free,
additive-free
conditions.
The
represents
a
practical
environmentally
friendly
approach
C–CF2
bond
formation
based
on
rearrangement
strategy,
which
will
find
potential
applications
among
drug
discovery
development.
Chemical Communications,
Год журнала:
2020,
Номер
56(12), С. 1815 - 1818
Опубликована: Янв. 1, 2020
The
first
example
of
visible
light
promoted
fluoroalkylation
reactions
initiated
via
noncovalent
interactions
between
acetone
and
fluoroalkyl
iodides
is
presented.
reaction
system
features
synthetic
simplicity,
mild
conditions
without
any
photoredox
catalyst,
high
functional
group
tolerance.
A
wide
range
substrate
scopes
such
as
alkenes,
alkynes
(hetero)arenes
were
all
compatible
with
the
system.
Advanced Synthesis & Catalysis,
Год журнала:
2019,
Номер
361(10), С. 2354 - 2359
Опубликована: Март 12, 2019
Abstract
A
copper‐catalyzed
direct
C−H
difluoroacetylation
of
quinoxalinones
at
the
C‐3
position
with
ethyl
bromodifluoroacetate
has
been
developed.
In
this
reaction,
diverse
difluoroacetylated
quinoxalin‐2(1
H
)‐ones
a
wide
range
functional
groups
could
be
obtained
in
moderate
to
good
yields,
using
cheap,
commercially
available
reagents.
This
protocol
would
offer
meaningfully
synthetic
method
for
pharmacologically
interesting
)‐one
derivatives.
magnified
image
Organic Letters,
Год журнала:
2022,
Номер
24(46), С. 8542 - 8546
Опубликована: Ноя. 14, 2022
An
aryl
disulfide
mediated
C-F
bond
activation
of
the
trifluoromethyl
group
to
generate
valuable
gem-difluoroalkylindoles
is
described.
This
method
relies
on
readily
available
commodity
reagents
under
mild
reaction
conditions
and
represents
first
transition-metal-free
redox-neutral
strategy.
The
employs
various
substituted
indoles
α-fluoro-substituted
esters.
Further,
this
mode
was
also
amenable
trifluoromethylated
arenes
for
preparation
bis-benzylic
gem-difluoromethylenes
between
indole
arene
substructures,
providing
access
a
unique
chemical
space.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2119 - 2123
Опубликована: Март 4, 2024
A
green
and
highly
efficient
visible-light-induced
radical
cascade
difluoroalkylation/cyclization
reaction
of
N-cyanamide
alkenes
has
been
developed.
variety
CF2COR-containing
quinazolinones
have
obtained
in
high
yields
with
cheap
non-metallic
4CzIPN
as
the
photocatalyst.
This
photocatalytic
provides
rapid,
facile,
practical
access
to
valuable
polycyclic
quinazolinone,
it
is
amenable
gram
scale.
