The Chemical Record,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 17, 2024
Abstract
The
transition
metal
catalyzed
coupling
reaction
has
revolutionized
the
strategies
for
forging
carbon‐carbon
bonds.
In
contrast
to
traditional
cross‐coupling
methods
using
pre‐prepared
nucleophilic
organometallic
reagents,
reductive
reactions
C−C
bonds
formation
provide
some
advantages.
Because
both
partners
are
reduced
in
final
products
a
stoichiometric
amount
of
reductant,
this
approach
not
only
avoids
need
use
sensitive
species,
but
also
provides
an
orthogonal
and
complementary
access
classical
reaction.
Notably,
feature
readily
available
fragments,
promote
good
step
economy,
exhibit
high
functional
group
tolerance
unique
chemoselectivity,
which
have
propelled
their
increasingly
popular
organic
synthesis.
recent
years,
due
low
price,
minimal
toxicity,
environmentally
benign
character,
iron‐catalyzed
garnered
significant
attention
from
synthetic
chemists
pharmacologists,
especially
coupling.
This
review
aims
insightful
overview
advances
reactions,
illustrate
possible
mechanisms.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Jan. 29, 2024
Abstract
We
highlight
key
contributions
in
the
field
of
direct
radical
C
Ar
−
H
(hetero)aromatic
functionalization
involving
fluorinated
radicals.
A
compilation
Functional
Group
Transfer
Reagents
and
their
diverse
activation
mechanisms
leading
to
release
radicals
are
discussed.
The
substrate
scope
for
each
is
analyzed
classified
into
three
categories
according
electronic
properties
substrates.
Density
functional
theory
computational
analysis
provides
insights
chemical
reactivity
several
through
electrophilicity
nucleophilicity
parameters.
Theoretical
reduction
potentials
also
highlights
remarkable
correlation
between
oxidizing
ability.
It
established
that
highly
(e.g.
⋅OCF
3
)
capable
engaging
single‐electron
transfer
(SET)
processes
rather
than
addition,
which
good
agreement
with
experimental
literature
data.
scale,
based
on
barrier
addition
these
benzene
elaborated
using
high
accuracy
DLPNO‐(U)CCSD(T)
method.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9045 - 9062
Published: March 15, 2024
Methods
for
the
synthesis
of
α-branched
alkylamines
are
important
due
to
their
ubiquity
in
biologically
active
molecules.
Despite
development
many
methods
amine
preparation,
C(sp3)-rich
nitrogen-containing
compounds
continue
pose
challenges
synthesis.
While
carbonyl
reductive
amination
(CRA)
between
ketones
and
is
cornerstone
method
alkylamine
synthesis,
it
sometimes
limited
by
sterically
demanding
condensation
step
dialkyl
amines
more
restricted
availability
compared
aldehydes.
We
recently
reported
a
"higher-order"
variant
this
transformation,
alkylative
(CAA),
which
utilized
halogen
atom
transfer
(XAT)-mediated
radical
mechanism,
enabling
streamlined
complex
alkylamines.
efficacy
visible-light-driven
approach,
displayed
scalability
issues,
competitive
was
problem
certain
substrate
classes,
limiting
applicability.
Here,
we
report
change
reaction
regime
that
expands
CAA
platform
through
realization
an
extremely
broad
zinc-mediated
reaction.
This
new
strategy
enabled
elimination
CRA,
simplified
purification,
improved
scope.
Furthermore,
harnessed
carboxylic
acid
derivatives
as
alkyl
donors
facilitated
α-trialkyl
tertiary
amines,
cannot
be
accessed
via
CRA.
Zn-mediated
can
carried
out
at
variety
scales,
from
10
μmol
setup
microtiter
plates
high-throughput
experimentation,
gram-scale
medicinally-relevant
compounds.
believe
transformation
enables
robust,
efficient,
economical
access
provides
viable
alternative
current
benchmark
methods.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
The
first
bottleable
example
of
a
neutral
Group
13
atom
bound
only
by
donor
ligands
(L)
has
been
fully
characterized
spectroscopic
methods
and
its
structure
determined
single-crystal
X-ray
diffraction
study.
A
two-coordinate
paramagnetic
L2B0
complex
can
readily
be
accessed
through
facile
reduction
reaction
is
stabilized
π-accepting
cyclic
(alkyl)(amino)carbene
(CAAC)
ligands.
Further
(CAAC)2B
leads
to
the
isolation
stable
diamagnetic
boride
anion.
In
turn,
oxidation
putative
formation
transient
cationic
borylene,
which
trapped
form
boron(I)
complex.
Density
functional
theory
calculations
support
formulation
as
boron(0)
strong
multiple
bonding.
Russian Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
92(12), P. RCR5104 - RCR5104
Published: Dec. 1, 2023
After
the
appearance
of
green
chemistry
concept,
which
was
introduced
in
vocabulary
early
1990s,
its
main
statements
have
been
continuously
developed
and
modified.
Currently,
there
are
10–12
cornerstones
that
should
form
basis
for
an
ideal
chemical
process.
This
review
analyzes
accumulated
experience
achievements
towards
design
products
processes
reduce
or
eliminate
use
generation
hazardous
substances.
The
presents
views
leading
Russian
scientists
specializing
various
fields
this
subject,
including
homogeneous
heterogeneous
catalysis,
fine
basic
organic
synthesis,
electrochemistry,
polymer
chemistry,
based
on
bio-renewable
feedstocks
energetic
compounds
materials.
A
new
approach
to
quantitative
evaluation
environmental
friendliness
by
authors
is
described.
<br>
bibliography
includes
1761.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(8), P. 4822 - 4862
Published: April 2, 2024
The
synthesis
of
organic
compounds
efficiently
via
fewer
steps
but
in
higher
yields
is
desirable
as
this
reduces
energy
and
reagent
use,
waste
production,
thus
environmental
impact
well
cost.
reactivity
C–H
bonds
ortho
to
fluorine
substituents
(poly)fluoroarenes
with
metal
centers
enhanced
relative
meta
para
positions.
Thus,
direct
functionalization
without
prefunctionalization
becoming
a
significant
area
research
chemistry.
Novel
selective
methodologies
functionalize
(poly)fluorinated
arenes
by
taking
advantage
the
C–F
are
continuously
being
developed.
This
review
summarizes
reasons
for
consequent
developments
valuable
(poly)fluoroarene-containing
compounds.
Green Synthesis and Catalysis,
Journal Year:
2024,
Volume and Issue:
5(4), P. 211 - 269
Published: May 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.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 18, 2024
Catalysed
C-H
activation
has
emerged
as
a
transformative
platform
for
molecular
synthesis
and
provides
new
opportunities
in
drug
discovery
by
late-stage
functionalisation
(LSF)
of
complex
molecules.
Notably,
small
aliphatic
motifs
have
gained
significant
interest
medicinal
chemistry
their
beneficial
properties
applications
sp
