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.
Chemical Communications,
Год журнала:
2024,
Номер
60(28), С. 3764 - 3773
Опубликована: Янв. 1, 2024
This
feature
article
summarizes
our
efforts
towards
developing
Rh-catalyzed
reactions
of
gem
-difluorinated
cyclopropanes,
briefly
discussing
the
design,
selectivity,
mechanisms
and
future
research
prospects.
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2500 - 2566
Опубликована: Окт. 9, 2024
With
the
resurgence
of
electrosynthesis
in
organic
chemistry,
there
is
a
significant
increase
number
routes
available
for
late-stage
functionalization
(LSF)
drugs.
Electrosynthetic
methods,
which
obviate
need
hazardous
chemical
oxidants
or
reductants,
offer
unprecedented
control
reactions
through
continuous
variation
applied
potential
and
possibility
combination
with
photochemical
processes.
This
capability
substantial
advantage
performing
electrochemical
photoelectrochemical
LSF.
Ultimately,
these
protocols
are
poised
to
become
vital
component
medicinal
chemist's
toolkit.
In
this
review,
we
discuss
that
have
been
demonstrated
be
applicable
LSF
pharmaceutical
drugs,
their
derivatives,
natural
substrates.
We
present
analyze
representative
examples
illustrate
electrochemistry
photoelectrochemistry
valuable
molecular
scaffolds.
Green Chemistry,
Год журнала:
2023,
Номер
25(23), С. 9672 - 9679
Опубликована: Янв. 1, 2023
A
H
2
O-promoted
and
(NH
4
)
CO
3
-enabled
defluoroiminization
reaction
of
fluoroalkyl
alkenes
for
the
synthesis
fluoroalkylated
1,5-diazapentadienes
has
been
developed.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 9020 - 9024
Опубликована: Дек. 8, 2023
This
study
presents
a
novel
method
for
the
regioselective
coupling
of
gem-difluorinated
cyclopropanes
with
gem-diborylmethane,
utilizing
Pd-catalyst
system.
innovative
approach
enables
synthesis
2-fluoroalkenyl
monoboronate
scaffolds
high
Z-selectivity.
The
resulting
products
undergo
further
transformations,
including
oxidation,
Suzuki
cross-coupling,
and
trifluoroborylation,
all
which
are
achieved
good
yields.
work
introduces
valuable
synthetic
pathway
to
access
important
fluorinated
compounds
various
applications
in
organic
chemistry.
Abstract
Transition‐metal
(TM)
catalyzed
reaction
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
has
drawn
much
attention
recently.
The
generally
occurs
via
the
activation
distal
C─C
bond
in
‐DFCPs
by
a
low‐valent
TM
through
oxidative
addition,
eventually
producing
mono‐fluoro
olefins
as
coupling
products.
However,
achieving
regioselective
proximal
that
overcomes
intrinsic
reactivity
catalysis
remains
elusive.
Here,
new
mode
enabled
high‐valent
copper
catalysis,
which
allows
exclusive
congested
is
presented.
achieves
fluoroarylation
uses
NFSI
(N‐fluorobenzenesulfonimide)
electrophilic
fluoro
reagent
and
arenes
C─H
nucleophiles,
enabling
synthesis
diverse
CF
3
‐containing
scaffolds.
It
proposed
species
plays
an
important
role
possibly
σ‐bond
metathesis.
Chemical Science,
Год журнала:
2024,
Номер
15(34), С. 13800 - 13806
Опубликована: Янв. 1, 2024
Metathesis
reactions
have
been
established
as
a
powerful
tool
in
organic
synthesis.
While
great
advances
were
achieved
double-bond
metathesis,
like
olefin
metathesis
and
carbonyl
single-bond
has
received
less
attention
the
past
decade.
Herein,
we
describe
first
C(sp
Organic Letters,
Год журнала:
2023,
Номер
25(33), С. 6143 - 6148
Опубликована: Авг. 16, 2023
Herein,
we
have
successfully
developed
a
convergent
paired
electrolysis
strategy
for
the
defluorinative
thiolation
process
utilizing
thiols
and
gem-difluoroalkenes
as
precursors.
This
protocol
exhibits
remarkable
tolerance
toward
wide
range
of
functional
groups,
exemplified
by
successful
late-stage
defluorothiolation
complex
molecules.
Additionally,
this
is
amenable
to
gram-scale
synthesis,
making
use
both
anodic
oxidation
cathodic
reduction
processes
in
an
efficient
manner.
Several
control
studies
were
conducted
suggested
mechanism.
