Chemical Science,
Год журнала:
2023,
Номер
14(9), С. 2379 - 2385
Опубликована: Янв. 1, 2023
The
development
of
strategies
for
single
and
selective
C-F
bond
activation
represents
an
important
avenue
to
overcome
limitations
in
the
synthesis
valuable
fluorine-containing
compounds.
synthetic
medicinal
research
communities
would
benefit
from
new
routes
that
access
such
relevant
molecules
a
simple
manner.
Herein
we
disclose
straightforward
mechanistically
distinct
pathway
generate
gem-difluoromethyl
radicals
their
installation
onto
N-arylmethacrylamides
preparation
difluorinated
oxindole
derivatives.
To
achieve
operational
simplicity,
use
readily
available
benzenethiol
as
photocatalyst
under
open-to-air
conditions
was
developed,
demonstrating
facile
multigram
targeted
fluorinated
molecules.
Additionally,
dispersion-corrected
density
functional
theory
(DFT)
empirical
investigations
provide
basis
support
proposed
reaction
pathway,
indicating
arene
thiolate
is
efficient
organophotocatalyst
this
transformation.
Advanced Sustainable Systems,
Год журнала:
2022,
Номер
6(9)
Опубликована: Июль 6, 2022
Abstract
Solar
energy
is
a
green,
sustainable,
and
de
facto
inexhaustible
source
for
mankind.
The
conversion
of
solar
into
other
forms
has
attracted
extensive
research
interest
due
to
climate
change
the
crisis.
Among
all
technologies,
photothermal
exhibits
unique
advantages
when
applied
water
purification,
desalination,
high‐temperature
heterogeneous
catalysis,
anti‐bacterial
treatments,
deicing.
In
this
review,
various
mechanisms
based
on
different
heat
release
are
summarized
some
latest
examples
presented.
addition,
necessary
prerequisites
solar‐driven
materials
toward
their
practical
applications
also
discussed.
Further,
advances
in
discussed,
focusing
types
applications.
Finally,
summary
given
challenges
opportunities
This
review
aims
give
comprehensive
understanding
emerging
technologies
effect,
especially
by
using
nanomaterials
nanostructures.
ACS Catalysis,
Год журнала:
2022,
Номер
12(7), С. 4103 - 4109
Опубликована: Март 18, 2022
Thiol
is
known
to
act
as
a
hydrogen
atom
transfer
catalyst
working
in
synergy
with
photocatalyst
photoredox
catalysis,
but
we
report
herein
that
an
arene
thiolate
appropriate
substituent
can
be
photoactivated
under
visible
light
function
both
strongly
reducing
electron-donating
redox
and
HAT
enable
catalytic
C–F
activation
of
trifluoromethyl
substrates
for
selective
hydrodefluorination
coupling
various
alkenes
the
presence
formate
salts.
These
reactions
demonstrate
promising
utility
arenethiolates
dual
photocatalysts.
The
synthetic
this
method
demonstrated
by
broad
scope
amenable
substrates,
including
trifluoromethylated
(hetero)arenes,
trifluoroacetates,
trifluoroacetamides,
which
exhibited
high
levels
chemoselectivity.
reaction
efficacy
allows
site-selective
late-stage
functionalization
multitrifluoromethylated
bioactive
compounds
pharmaceuticals
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 2149 - 2155
Опубликована: Янв. 25, 2023
Herein,
a
photocatalytic
strategy
for
the
synthesis
of
succinic
acids
by
alkene
dicarboxylation
with
carbon
dioxide
(CO2)
and
formate
salt
as
synergistic
sources
is
described.
The
acts
both
C1
source
reductant
in
reaction
catalytic
amount
1,4-diazabicyclo[2.2.2]octane
(DABCO)
hydrogen
atom
transfer
reagent.
Various
mono-,
di-,
trisubstituted
alkenes,
acrylate,
acrylamide,
indole
derivatives
could
be
converted
to
corresponding
diacids,
which
provided
potential
useful
applications
medicinal
chemistry
polymer
industry.
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 15991 - 16011
Опубликована: Ноя. 28, 2023
Carbon
dioxide
radical
anion
(CO2•–)
is
a
highly
reactive
nucleophilic
species
that
has
recently
emerged
in
organic
chemistry
as
strong
single
electron
donor
(reductant)
and
reactant
for
the
synthesis
of
carboxylic
acids.
In
general,
CO2•–
can
be
generated
by
either
direct
reduction
CO2
or
HAT
formate
salts.
Achievements
reactions
involving
have
been
witnessed
recent
years.
This
Review
summarizes
advances
highlighting
some
challenges
identifying
potential
areas
improvement,
which
may
offer
inspiration
future
studies.
ACS Catalysis,
Год журнала:
2023,
Номер
13(4), С. 2482 - 2488
Опубликована: Фев. 3, 2023
The
radical
anion
of
CO2
(CO2•–)
is
a
strongly
nucleophilic
species
with
rapidly
emerging
applications
in
contemporary
organic
chemistry.
This
exhibits
high
reactivity
single-electron
reduction
reactions
due
to
the
concomitant
release
stable
CO2,
or
Giese-type
reactions,
especially
for
electron-deficient
alkenes
and
styrene
derivatives.
In
contrast
previous
reports,
we
herein
disclose
development
robust
method
introduction
CO2•–,
which
can
be
generated
from
cesium
formate
under
photoredox/hydrogen
atom
transfer
(HAT)
catalysis,
into
heteroaromatics
such
as
benzofuran,
benzothiophene,
indole
derivatives
afford
synthetically
useful
α-oxy,
α-thio,
α-amino
acid
moderate
yield.
addition,
when
using
naphthalene
derivatives,
both
addition
occur
simultaneously
produce
carboxylated
tetrahydronaphthalene
good
Moreover,
one
tetrahydronaphthalenes
that
bear
cyano
group
was
transformed
corresponding
γ-butyrolactam
via
functionality
through
hydrogenation
followed
by
cyclization.
To
best
our
knowledge,
these
dearomative
carboxylation
metal
formates
photoredox/HAT
conditions
are
unprecedented,
thus
providing
synthetic
option
C1
source
(hetero)aromatics.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(1), С. 263 - 316
Опубликована: Дек. 7, 2023
The
employment
of
light
and/or
electricity
-
alternatively
to
conventional
thermal
energy
unlocks
new
reactivity
paradigms
as
tools
for
chemical
substrate
activations.
This
leads
the
development
synthetic
reactions
and
a
vast
expansion
spaces.
review
summarizes
recent
developments
in
photo-
electrochemical
activation
strategies
functionalization
strong
bonds
particularly
carbon-heteroatom
(C-X)
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Янв. 10, 2024
Abstract
Bioisosteric
design
has
become
an
essential
approach
in
the
development
of
drug
molecules.
Recent
advancements
synthetic
methodologies
have
enabled
rapid
adoption
this
strategy
into
discovery
programs.
Consequently,
conceptionally
innovative
practices
would
be
appreciated
by
medicinal
chemistry
community.
Here
we
report
expeditous
method
for
synthesizing
aryl
difluoromethyl
bicyclopentane
(ADB)
as
a
bioisostere
benzophenone
core.
This
involves
merger
light-driven
C−F
bond
activation
and
strain-release
under
catalysis
newly
designed
N
-anionic-based
organic
photocatalyst.
defluorinative
coupling
methodology
enables
direct
conversion
wide
variety
commercially
available
trifluoromethylaromatic
bonds
(more
than
70
examples)
corresponding
bicyclo[1.1.1]pentanes
(BCP)
arenes/difluoromethyl
BCP
boronates
single
step.
The
can
also
applied
to
[3.1.1]and
[4.1.1]propellane
systems,
providing
access
analogues
with
different
geometries.
Moreover,
successfully
used
protocol
rapidly
prepare
ADB-substituted
bioactive
molecule
Adiporon.
Biological
testing
shown
that
ADB
scaffold
potential
enhance
pharmacological
properties
benzophenone-type
candidates.
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.
