Abstract
The
difluoromethyl
group
(CF2H)
can
function
as
a
lipophilic
hydrogen-bond
donor,
and
is
regarded
bioisostere
of
functional
groups
such
hydroxy
(-OH),
thiol
(-SH),
amino
(-NH2).
unique
physicochemical
properties
this
make
difluoromethylation
hot
topic
in
the
field
synthetic
organic
chemistry,
recent
decades,
various
methods
have
been
developed
for
constructing
C(sp3)—CF2H,
C(sp2)—CF2H,
C(sp)
—CF2H,
X—CF2H
(X
=
N,
O,
S,
Se,
B,
P,
etc.)
bonds.
This
review
summarizes
currently
available
reagents
performing
reactions,
well
other
approaches
installing
unit.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(16)
Published: Jan. 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.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(15)
Published: Feb. 14, 2024
Abstract
Fluorinated
small
molecules
are
commonly
used
in
functional
small‐molecule
chemistry,
and
N
‐difluoromethyl
(
‐CF
2
H)
compounds
particularly
intriguing
due
to
their
unique
unexplored
physiochemical
properties.
However,
despite
limited
progress,
a
general
methodological
approach
the
synthesis
of
H
remains
elusive.
Here,
guided
by
computation,
we
present
simple
practical
protocol
access
amides
related
carbonyl
derivatives.
The
involves
one‐pot
conversion
thioformamides
through
desulfurization‐fluorination
acylation,
providing
‐difluoromethylcarbamoyl
fluoride
building
blocks
that
can
be
further
diversified
variety
with
rich
functionality.
Additionally,
preliminary
studies
on
properties
stability
showcased
potential
application
pharmaceuticals
agrochemicals.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(31), P. 6714 - 6719
Published: July 26, 2024
Sulfamoyl
fluorides,
as
a
crucial
building
block
of
SuFEx,
have
garnered
extensive
research
interest
due
to
their
unique
properties.
However,
the
direct
radical
fluorosulfonamidation
process
for
synthesis
sulfamoyl
fluorides
has
been
overlooked.
We
herein
disclosed
practical
procedure
constructing
redox-active
fluorosulfonamide
reagent
named
fluorosulfonyl-N-pyridinium
tetrafluoroborate
(PNSF)
from
SO2F2.
These
reagents
can
facilitate
range
reactions,
including
N-(fluorosulfonyl)
sulfonamidation
(hetero)arenes,
sequential
stereoselective
fluorosulfonamidation,
and
1,2-difunctionalization
alkenes.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
We
developed
a
mild,
rapid
process
employing
AgF
and
thioamides
to
produce
α,α-difluoromethylene
amines
efficiently.
This
method
exhibited
remarkable
tolerance
toward
various
functional
groups
present
in
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 12, 2024
Abstract
Nitrogen‐centered
radicals
(NCRs)
have
gained
significant
attention
due
to
their
high
reactivity,
which
facilitates
many
useful
and
challenging
transformations,
particularly
in
the
formation
of
C−N
bonds.
In
this
regard,
N
‐aminopridinium
reagents
are
easily
accessible
substrates
that
readily
generate
‐centered
radicals,
can
be
trapped
by
arenes,
olefins,
alkynes
even
alkanes
under
visible
light
irradiation.
recent
years,
amination
strategies
involving
‐aminopyridinium
salts
grown
remarkably
attracted
considerable
interest
within
synthetic
community.
This
review
comprehensively
includes
all
advances
bond
construction
via
derived
from
substrates.
Abstract
The
difluoromethyl
group
(CF2H)
can
function
as
a
lipophilic
hydrogen-bond
donor,
and
is
regarded
bioisostere
of
functional
groups
such
hydroxy
(-OH),
thiol
(-SH),
amino
(-NH2).
unique
physicochemical
properties
this
make
difluoromethylation
hot
topic
in
the
field
synthetic
organic
chemistry,
recent
decades,
various
methods
have
been
developed
for
constructing
C(sp3)—CF2H,
C(sp2)—CF2H,
C(sp)
—CF2H,
X—CF2H
(X
=
N,
O,
S,
Se,
B,
P,
etc.)
bonds.
This
review
summarizes
currently
available
reagents
performing
reactions,
well
other
approaches
installing
unit.
