Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(7), С. 4380 - 4392
Опубликована: Фев. 1, 2024
The
hydrofluorination
of
alkenes
represents
an
attractive
strategy
for
the
synthesis
aliphatic
fluorides.
This
approach
provides
a
direct
means
to
form
C(sp3)–F
bonds
selectively
from
readily
available
alkenes.
Nonetheless,
conducting
using
nucleophilic
fluorine
sources
poses
significant
challenges
due
low
acidity
and
high
toxicity
associated
with
HF
poor
nucleophilicity
fluoride.
In
this
study,
we
present
new
Co(salen)-catalyzed
simple
utilizing
Et3N·3HF
as
sole
source
both
hydrogen
fluorine.
process
operates
via
photoredox-mediated
polar-radical-polar
crossover
mechanism.
We
also
demonstrated
versatility
method
by
effectively
converting
diverse
array
activated
varying
degrees
substitution
into
hydrofluorinated
products.
Furthermore,
successfully
applied
methodology
18F-hydrofluorination
reactions,
enabling
introduction
18F
potential
radiopharmaceuticals.
Our
mechanistic
investigations,
conducted
rotating
disk
electrode
voltammetry
DFT
calculations,
unveiled
involvement
carbocation
CoIV–alkyl
species
viable
intermediates
during
fluorination
step,
contribution
each
pathway
depends
on
structure
starting
alkene.
Journal of Medicinal Chemistry,
Год журнала:
2015,
Номер
58(21), С. 8315 - 8359
Опубликована: Июль 22, 2015
The
role
of
fluorine
in
drug
design
and
development
is
expanding
rapidly
as
we
learn
more
about
the
unique
properties
associated
with
this
unusual
element
how
to
deploy
it
greater
sophistication.
judicious
introduction
into
a
molecule
can
productively
influence
conformation,
pKa,
intrinsic
potency,
membrane
permeability,
metabolic
pathways,
pharmacokinetic
properties.
In
addition,
18F
has
been
established
useful
positron
emitting
isotope
for
use
vivo
imaging
technology
that
potentially
extensive
application
discovery
development,
often
limited
only
by
convenient
synthetic
accessibility
labeled
compounds.
wide
ranging
applications
are
providing
strong
stimulus
new
methodologies
allow
facile
access
range
fluorinated
review,
provide
an
update
on
effects
strategic
incorporation
molecules
emission
tomography.
Chemical Reviews,
Год журнала:
2017,
Номер
117(18), С. 11796 - 11893
Опубликована: Июнь 1, 2017
Flow
chemistry
involves
the
use
of
channels
or
tubing
to
conduct
a
reaction
in
continuous
stream
rather
than
flask.
equipment
provides
chemists
with
unique
control
over
parameters
enhancing
reactivity
some
cases
enabling
new
reactions.
This
relatively
young
technology
has
received
remarkable
amount
attention
past
decade
many
reports
on
what
can
be
done
flow.
Until
recently,
however,
question,
"Should
we
do
this
flow?"
merely
been
an
afterthought.
review
introduces
readers
basic
principles
and
fundamentals
flow
critically
discusses
recent
accounts.
Chemical Society Reviews,
Год журнала:
2018,
Номер
47(15), С. 5786 - 5865
Опубликована: Янв. 1, 2018
This
review
provides
an
overview
of
the
use
electrochemistry
as
appealing
platform
for
expediting
carbon–hydrogen
functionalization
and
carbon–nitrogen
bond
formation.
Chemical Reviews,
Год журнала:
2018,
Номер
118(7), С. 3887 - 3964
Опубликована: Апрель 2, 2018
New
methods
for
preparation
of
tailor-made
fluorine-containing
compounds
are
in
extremely
high
demand
nearly
every
sector
chemical
industry.
The
asymmetric
construction
quaternary
C-F
stereogenic
centers
is
the
most
synthetically
challenging
and,
consequently,
least
developed
area
research.
As
a
reflection
this
apparent
methodological
deficit,
pharmaceutical
drugs
featuring
constitute
less
than
1%
all
medicines
currently
on
market
or
clinical
development.
Here
we
provide
comprehensive
review
current
research
activity
area,
including
such
general
directions
as
electrophilic
fluorination
via
organocatalytic
and
transition-metal
catalyzed
reactions,
elaboration
substrates
alkylations,
Mannich,
Michael,
aldol
additions,
cross-coupling
biocatalytic
approaches.
Journal of the American Chemical Society,
Год журнала:
2017,
Номер
139(6), С. 2484 - 2503
Опубликована: Янв. 17, 2017
This
Article
details
the
development
of
iron-catalyzed
conversion
olefins
to
radicals
and
their
subsequent
use
in
construction
C–C
bonds.
Optimization
a
reductive
diene
cyclization
led
an
intermolecular
cross-coupling
electronically-differentiated
donor
acceptor
olefins.
Although
substitution
on
was
initially
limited
alkyl
aryl
groups,
additional
efforts
culminated
expansion
scope
various
heteroatom-based
functionalities,
providing
unified
olefin
reactivity.
A
vinyl
sulfone
developed,
which
allowed
for
efficient
synthesis
adducts
that
could
be
used
as
branch
points
further
diversification.
Moreover,
this
reactivity
extended
into
olefin-based
Minisci
reaction
functionalize
heterocyclic
scaffolds.
Finally,
mechanistic
studies
resulted
more
thorough
understanding
reaction,
giving
rise
second-generation
set
conditions.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(42), С. 14824 - 14848
Опубликована: Фев. 13, 2019
Abstract
This
Review
summarizes
advances
in
fluorination
by
C(sp
2
)−H
and
3
activation.
Transition‐metal‐catalyzed
approaches
championed
palladium
have
allowed
the
installation
of
a
fluorine
substituent
at
)
sites,
exploiting
reactivity
high‐oxidation‐state
transition‐metal
fluoride
complexes
combined
with
use
directing
groups
(some
transient)
to
control
site
stereoselectivity.
The
large
majority
known
methods
employ
electrophilic
reagents,
but
combining
nucleophilic
source
an
oxidant
appeared.
External
ligands
proven
be
effective
for
directed
weakly
coordinating
auxiliaries,
thereby
enabling
over
reactivity.
Methods
relying
on
formation
radical
intermediates
are
complementary
transition‐metal‐catalyzed
processes
as
they
allow
undirected
fluorination.
To
date,
C−H
fluorinations
mainly
N−F
reagents
unique
Mn
III
‐catalyzed
oxidative
using
has
been
developed.
Overall,
field
late‐stage
progressed
much
more
slowly,
state
play
explaining
why
18
F‐fluorination
is
still
its
infancy.
Angewandte Chemie International Edition,
Год журнала:
2017,
Номер
57(3), С. 744 - 748
Опубликована: Ноя. 8, 2017
Abstract
A
photoinduced
cascade
strategy
leading
to
a
variety
of
differentially
functionalised
nitriles
and
ketones
has
been
developed.
These
reactions
rely
on
the
oxidative
generation
iminyl
radicals
from
simple
oximes.
Radical
transposition
by
C(sp
3
)−(sp
)
)−H
bond
cleavage
gives
access
distal
carbon
that
undergo
S
H
2
functionalisations.
mild,
visible‐light‐mediated
procedures
can
be
used
for
remote
fluorination,
chlorination,
azidation,
were
applied
modification
bioactive
structurally
complex
molecules.
Angewandte Chemie International Edition,
Год журнала:
2016,
Номер
55(8), С. 2743 - 2747
Опубликована: Янв. 21, 2016
The
radical
fluoroalkylation
of
isocyanides
with
fluorinated
sulfones
is
enabled
by
visible-light
photoredox
catalysis.
A
wide
range
readily
available
mono-,
di-,
and
trifluoromethyl
heteroaryl
can
thus
be
used
as
efficient
reagents
under
mild
conditions.
This
method
not
only
describes
a
new
synthetic
application
sulfones,
but
also
provides
route
to
fluoroalkyl
radicals.
Chemical Reviews,
Год журнала:
2017,
Номер
118(9), С. 4541 - 4572
Опубликована: Сен. 8, 2017
The
fundamental
advantages
and
potential
benefits
of
flow
microreactor
technology
include
extremely
large
surface-to-volume
ratios,
precise
control
over
temperature
residence
time,
fast
molecular
diffusion,
increased
safety
during
reactive
processes.
These
can
be
applied
to
a
wide
range
electrosynthetic
techniques,
so
the
integration
microreactors
with
electrosynthesis
has
received
significant
research
interest
from
both
academia
industry.
This
review
presents
an
up-to-date
overview
processes
in
continuous-flow
microreactors.
In
addition,
electrochemistry
are
discussed,
along
thorough
comparison
microreactor-based
conventional
batch
reaction
systems.
