Green Synthesis and Catalysis,
Год журнала:
2024,
Номер
5(4), С. 211 - 269
Опубликована: Май 6, 2024
The
development
of
catalytic
carbonylation
reactions
has
increased
considerably.
Although
many
reviews/chapters/books
on
have
been
published,
summaries
cheap
metal-catalyzed
aryl
halides
and
other
chemical
bonds
with
high
dissociation
energy
C-Y
(Y
=
O,
N,
H)
are
still
very
rare.
Focusing
green
sustainable
chemistry,
this
review
summarizes
discusses
the
achievements
carbonylative
transformations
(C(sp2)-X)
strong
based
non-expensive
metal
catalysts
(Co,
Mn,
Mo,
Ni,
Fe,
Cu),
photochemical
electrochemical
systems
developed
in
recent
decades.
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(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.
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.
Chemical Science,
Год журнала:
2024,
Номер
15(8), С. 2712 - 2724
Опубликована: Янв. 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'.
Organic Letters,
Год журнала:
2022,
Номер
24(22), С. 4075 - 4080
Опубликована: Июнь 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.
