The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7790 - 7794
Опубликована: Май 29, 2024
The
incorporation
of
difluoromethylene
groups
into
aza-heterocycles
represents
a
compelling
yet
underexplored
avenue
in
contemporary
chemical
research.
In
this
study,
we
unveil
hybrid
palladium-catalyzed
intramolecular
gem-difluoroalkylamination
conjugated
dienes,
providing
versatile
approach
to
the
synthesis
diverse
functionalized
pyrrolidines.
Noteworthy
features
include
mild
reaction
conditions
and
remarkable
tolerance
toward
various
functional
groups.
Additionally,
use
alkyl
iodides
as
electrophiles
facilitates
generation
corresponding
alkylamination
products.
Control
experiments
support
proposed
radical–polar
crossover
pathway,
offering
insights
underlying
processes
governing
transformation.
Science,
Год журнала:
2021,
Номер
371(6535), С. 1232 - 1240
Опубликована: Март 5, 2021
Defluorinative
functionalization
of
readily
accessible
trifluoromethyl
groups
constitutes
an
economical
route
to
partially
fluorinated
molecules.
However,
the
controllable
replacement
one
or
two
fluorine
atoms
while
maintaining
high
chemoselectivity
remains
a
formidable
challenge.
Here
we
describe
general
strategy
for
sequential
carbon-fluorine
(C-F)
bond
functionalizations
trifluoroacetamides
and
trifluoroacetates.
The
reaction
begins
with
activation
carbonyl
oxygen
atom
by
4-dimethylaminopyridine-boryl
radical,
followed
spin-center
shift
trigger
C-F
scission.
A
chemoselectivity-controllable
two-stage
process
enables
generation
difluoro-
monofluoroalkyl
radicals,
which
are
selectively
functionalized
different
radical
traps
afford
diverse
products.
mechanism
origin
were
established
experimental
computational
approaches.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(34), С. 13971 - 13979
Опубликована: Авг. 19, 2021
Selective
functionalization
of
inactive
C(sp3)-F
bonds
to
prepare
medicinally
interesting
aryldifluoromethylated
compounds
remains
challenging.
One
promising
route
is
the
transition-metal-catalyzed
cross-coupling
through
oxidative
addition
bond
in
trifluoromethylarenes
(ArCF3),
which
are
ideal
precursors
for
this
process
due
their
ready
availability
and
low
cost.
Here,
we
report
an
unprecedented
excited-state
palladium
catalysis
strategy
selective
defluoroarylation
with
arylboronic
acids.
This
visible-light-induced
palladium-catalyzed
proceeds
under
mild
reaction
conditions
allows
transformation
a
variety
acids
ArCF3.
Preliminary
mechanistic
studies
reveal
that
ArCF3
palladium(0)
via
single
electron
transfer
pathway
responsible
activation.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
364(2), С. 234 - 267
Опубликована: Ноя. 29, 2021
Abstract
Fluorine‐containing
moieties
are
widely
used
in
the
pharmaceutical,
agrochemical,
and
material
fields.
Thus,
these
structures
of
immense
interest
fields
organic
synthesis
medicinal
chemistry.
Among
various
fluorinated
groups,
difluoromethyl
unit
has
drawn
increasing
attention
due
to
its
unique
pharmaceutical
properties.
In
recent
years,
several
methods
for
difluoromethylated
compounds
have
been
rapidly
developed.
However,
most
treat
aromatic
with
excess
difluoromethylating
reagents,
which
often
contain
organometallic
compounds,
so
transformations
generally
less
environmentally
friendly
atom‐economical.
this
review,
we
summarize
development
new
motifs
or
difluoroalkenes
from
trifluoromethylated
trifluoromethyl
alkenes
via
single
C(
sp
3
)−F
bond
cleavage.
magnified
image
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(16), С. 1913 - 1928
Опубликована: Апрель 24, 2024
Comprehensive
Summary
Organic
fluorine
compounds
are
ubiquitous
and
pivotally
important
organic
molecules,
yet
their
activation
transformation
have
long
been
a
formidable
challenge
due
to
the
high
energy
low
reactivity
of
C—F
bonds.
electrosynthesis,
an
environmentally
benign
synthetic
method
in
chemistry,
enables
myriad
chemical
transformations
without
need
for
external
redox
reagents.
In
recent
years,
electrochemistry
has
emerged
as
powerful
tool
achieving
bonds
fluorine‐containing
compounds.
This
review
aims
succinctly
recapitulate
latest
advancements
electrochemical
defluorinative
delve
into
reaction
design,
mechanistic
insights,
developmental
prospects
these
methods.
Key
Scientists
1959,
Lund
was
first
pioneer
electroreduction
CF
3
CH
group.
Electrochemistry
lately
provided
new
opportunities
efficient
conversion
fluorides.
2020,
Zhou
coworkers
discovered
carboxylation
α‐CF
alkenes.
Lambert
colleagues
reported
electrophotocatalytic
amination
aryl
Electrochemical
hydrodefluorination
trifluoromethylketones
developed
by
Lennox
2021.
same
year,
Wang
Guo
disclosed
radical
alkylation
alkenes
with
Katritzky
salts
alkyl
precursors.
Subsequently,
Wu
Liao
described
transition‐metal‐free,
site‐selective
arylation
polyfluoroarenes
(het)arenes
using
paired
electrophotocatalysis.
2023,
numerous
efforts
were
made
achieve
bond
activation.
Xia
organoboron‐controlled
chemoselective
sequential
(deutero)hydrodefluorination
trifluoroacetamides.
Green Chemistry,
Год журнала:
2021,
Номер
23(5), С. 2095 - 2103
Опубликована: Янв. 1, 2021
A
facile
electro-reductive
hydrodefunctionalization
system
employing
triethylamine
as
a
sacrificial
reductant
is
described,
and
the
selectivity
capability
of
reduction
can
be
conveniently
switched
by
simple
change
reaction
solvent.
ACS Catalysis,
Год журнала:
2022,
Номер
12(11), С. 6495 - 6505
Опубликована: Май 17, 2022
Controlling
the
selectivity
of
synthetically
useful
reactions
has
been
a
longstanding
objective
organic
chemistry.
We
report
regiodivergent
synthetic
protocol
allowing
access
to
diverse
fluorinated
1,5-dienes
through
Pd/NHC-catalyzed
ring-opening
allylation
gem-difluorocyclopropanes.
Density
functional
theory
(DFT)
calculations
on
regioselectivity-determining
transition
states
provided
critical
insight
into
design
NHC
ligand
for
switching
regioselectivity.
Consistent
with
DFT
predictions,
N-heterocyclic
carbene
(NHC)
ligands
bulky
ortho
substituents
favored
branched
allylation,
IHept
providing
>
20:1
branched/linear
less
hindered
such
as
IMes
thermodynamically
more
stable
linear
products.
were
able
carry
out
late-stage
modification
various
complex
molecules
using
this
protocol.
Our
ligand-controlled
approach
provides
efficient
regioisomeric
from
same
starting
materials
and
constitutes
valuable
addition
toolbox
diversity-oriented
synthesis.
