Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(8), P. 1371 - 1387
Published: March 11, 2022
Abstract
2‐Bromo‐3,3,3‐trifluoropropene
(BTP)
represents
a
highly
valuable
synthon
in
synthetic
chemistry,
and
has
been
widely
used
organic
synthesis,
mainly
including
addition
reactions,
cross‐coupling
cycloaddition
or
cyclization
S
N
2’
Stetter
reactions
for
the
construction
of
various
fluorinated
compounds.
In
this
review,
we
systematically
summarize
these
reactions;
their
mechanisms
are
also
discussed.
magnified
image
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Aug. 22, 2023
Abstract
Much
progress
has
been
made
in
the
development
of
methods
to
both
create
compounds
that
contain
C−F
bonds
and
functionalize
bonds.
As
such,
are
becoming
common
versatile
synthetic
functional
handles.
This
review
summarizes
advantages
defluorinative
functionalization
reactions
for
small
molecule
synthesis.
The
coverage
is
organized
by
type
carbon
framework
fluorine
attached
mono‐
polyfluorinated
motifs.
main
challenges,
opportunities
advances
discussed
each
class
organofluorine.
Most
text
focuses
on
case
studies
illustrate
how
defluorofunctionalization
can
improve
routes
targets
or
properties
enable
unique
mechanisms
reactions.
broader
goal
showcase
incorporating
exploiting
design
routes,
improvement
specific
advent
new
methods.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(7), P. 2112 - 2133
Published: Jan. 1, 2024
Organofluorine
compounds
are
of
high
value.
NHC-catalyzed
fluorination
and
fluoroalkylation
have
served
as
powerful
versatile
vehicles
for
accessing
the
related
organofluorines.
This
review
focuses
on
recent
developments
in
this
area.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(8), P. 2712 - 2724
Published: Jan. 1, 2024
Frustrated
Lewis
pair
(FLP)
bond
activation
chemistry
has
greatly
developed
over
the
last
two
decades
since
seminal
report
of
metal-free
reversible
hydrogen
activation.
Recently,
FLP
systems
have
been
utilized
to
allow
monoselective
C-F
(at
equivalent
sites)
in
polyfluoroalkanes.
The
problem
'over-defluorination'
functionalization
polyfluoroalkanes
(where
multiple
fluoro-positions
are
uncontrollably
functionalized)
a
long-standing
chemical
fluorocarbon
for
80
years.
mediated
is
complementary
other
solutions
address
and
offers
several
advantages
unique
opportunities.
This
perspective
highlights
some
these
opportunities
places
development
into
context
wider
effort
overcome
'over-defluorination'.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
gem-Difluorohomoallyl
amines,
an
important
class
of
gem-difluoroalkenes,
are
prevalent
moieties
in
many
bioactive
compounds.
However,
limited
methods
suitable
for
the
synthesis
this
type
compound
containing
secondary
amines.
Here,
we
display
a
photocatalytic
multicomponent
protocol
gem-difluoroalkenes
which
makes
use
readily
available
materials:
arylamines,
alkyl
aldehydes,
and
α-trifluoromethyl
alkenes.
Moreover,
ketones
amines
also
substrates.
Preliminary
mechanistic
experiments
indicate
that
key
α-amino
radical
was
involved,
generated
from
reduction
situ-formed
imines
(or
iminium
ions)
by
reduced
photocatalyst.
Subsequent
addition
to
alkenes
β-F
elimination
deliver
desired
products.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(22), P. 4075 - 4080
Published: June 1, 2022
We
describe
a
catalytic
strategy
for
direct
single
C(sp3)-F
bond
alkylation
of
trifluoromethylbenzimidazoles
under
photoinduced
thiol
catalysis
process.
The
CO2
radical
anion
(CO2•-)
proved
to
be
the
most
efficient
single-electron
reductant
realize
such
transformation.
spin-center
shift
generated
intermediate
is
key
step
in
realizing
C-F
activation
mild
conditions
with
high
efficiency.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(23), P. 4286 - 4291
Published: June 8, 2022
We
report
an
efficient
strategy
that
combines
organic
photoredox
and
hydrogen
atom
transfer
to
deliver
gem-difluoroallylsilanes
via
defluorinative
silylation
of
α-trifluoromethylstyrenes
using
hydrosilanes
as
silicon
sources.
This
protocol
provides
environmentally
friendly
approach
for
the
preparation
structurally
diverse
with
excellent
functional
group
compatibility
renders
it
suitable
late-stage
modification
bioactive
complex
molecules.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(7)
Published: Dec. 16, 2022
(Deuterium-labeled)
CF2
H-
and
CFH2
-moieties
are
of
high
interest
in
drug
discovery.
The
demand
for
the
incorporation
these
fluoroalkyl
moieties
into
molecular
structures
has
witnessed
significant
synthetic
progress,
particularly
(deutero)hydrodefluorination
CF3
-containing
compounds.
However,
controllable
replacement
fluorine
atoms
while
maintaining
chemoselectivity
remains
challenging.
Herein,
we
describe
development
a
selective
reaction
via
electrolysis.
exhibits
remarkable
control,
which
is
enabled
by
addition
different
organoboron
sources.
procedure
operationally
simple
scalable,
provides
access
one
step
to
high-value
building
blocks
application
medicinal
chemistry.
Furthermore,
density
functional
theory
(DFT)
calculations
have
been
carried
out
investigate
mechanism
rationalize
observed.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(15), P. 9410 - 9417
Published: July 18, 2022
Transition-metal-catalyzed
difunctionalization
of
olefins
constitutes
a
fertile
synthetic
platform
for
rapid
access
to
complex
molecules
from
bulk
chemicals.
However,
substrates
featuring
fluoroalkyl
substituents
are
rarely
employed
because
facile
β-fluoride
elimination
pathways.
Herein,
we
report
hydroalkylation
trifluoromethylalkenes
with
alkyl
halides
under
nickel
catalysis
that
enables
the
construction
1,1,1-trifluoropropane
derivatives.
The
common
pathway
is
suppressed
by
identifying
competent
proton
donor
favors
protonolysis
process.
Also,
unactivated
alkenes
could
be
readily
as
when
using
Ni/hydrosilane
catalytic
system.
