Synthesis,
Год журнала:
2022,
Номер
55(03), С. 433 - 442
Опубликована: Окт. 24, 2022
Abstract
A
modified
method
for
iron-catalyzed
C–C
bond
cleavage
and
amination
alkylation
of
nonactivated
cyclic
alcohols
has
been
developed.
Using
FeCl3
as
catalyst,
the
photoinduced
ligand-to-metal
charge
transfer
facilitates
generation
O-radicals
from
alcohols,
subsequent
β-scission,
finally
radical
trapping.
Compared
with
Fe(OR)3
catalysis,
this
mildly
base-free
system
could
enable
in
a
broader
substrate
scope
higher
yields.
Moreover,
proceeds
electron-deficient
olefins
under
these
conditions.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 1678 - 1685
Опубликована: Янв. 13, 2023
We
report
a
photoinduced
iron/copper
dual-catalytic
strategy
for
the
radical
decarboxylation
functionalization
of
aliphatic
carboxylic
acids.
The
ligand-to-iron
charge
transfer
process
under
light
was
initially
occurred
to
generate
an
unstabilized
alkyl
radical,
and
copper
catalyst
delivered
enabled
subsequent
coupling
reactions
form
C–N
or
C–C
bonds.
By
merging
iron-catalyzed
with
catalysis,
this
system
allows
smooth
conversion
wide
range
acids
amination,
decarboxylative
dehydrogenation,
alkylation
efficiently.
A
variety
complex
drug
natural
molecules
is
applicable,
suggesting
that
would
facilitate
rapid
compound
library
synthesis
benefit
discovery
pharmaceutical
agents.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(24), С. 4359 - 4391
Опубликована: Ноя. 7, 2023
Abstract
Amide
bond
construction
has
garnered
significant
interest
in
recent
decades
due
to
amides
being
one
of
the
most
prevalent
functional
groups
among
bioactive
molecules.
Out
thirty‐seven
new
drugs
approved
by
FDA
2022,
eleven
are
small
molecules
containing
at
least
amide
bond.
Additionally,
there
nineteen
large
as
drugs,
some
which
have
peptide
structures,
and
therefore,
also
bear
bonds.
In
years,
multiple
teams
embraced
challenge
developing
more
efficient
methods
for
formation.
This
dedication
led
numerous
publications
appearing
monthly
prestigious
journals,
showcasing
advancements
this
field.
The
primary
goal
review
is
present
viable
strategies
constructing
It
crucial
differentiate
between
formation
synthesis;
hence,
focus
on
describing
specific
forming
C(O)−N
particular,
concentrates
developed
within
last
six
years.
There
a
particular
emphasis
approaches
that
consider
thought
process
when
selecting
starting
materials
groups.
approach
ensures
coverage
all
common
chemical
transformations
yield
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(9)
Опубликована: Дек. 14, 2021
C-H
amination
and
amidation
by
catalytic
nitrene
transfer
are
well-established
typically
proceed
via
electrophilic
attack
of
nitrenoid
intermediates.
In
contrast,
the
insertion
(formal)
terminal
nitride
ligands
into
bonds
is
much
less
developed
nitrogen
atom
remains
unknown.
We
here
report
synthesis
a
formal
complex
palladium.
Photocrystallographic,
magnetic,
computational
characterization
support
assignment
as
an
authentic
metallonitrene
(Pd-N)
with
diradical
ligand
that
singly
bonded
to
Pd
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(33)
Опубликована: Июнь 22, 2023
Abstract
The
rapidly
growing
importance
of
green
hydrogen
and
renewable
carbon
resources
as
essential
feedstocks
for
sustainable
chemical
value
chains
opens
room
disruptive
innovations
regarding
production
processes.
fluctuation
variability
associated
with
non‐fossil
energy
raw
material
supply
holds
many
challenges
catalysts
to
cope
the
resulting
dynamics.
However,
new
opportunities
also
arise
once
catalyst
design
starts
aim
at
performance
that
is
“adaptive”
rather
than
“task‐specific”.
In
this
Scientific
Perspective,
we
propose
define
adaptivity
in
catalysis
on
basis
three
properties
are
reversibility,
rapidity,
robustness
(
R
3
rule).
Promising
strategies
selected
examples
described
substantiate
scientific
concept
highlight
its
potential
conversion.
Organic Letters,
Год журнала:
2022,
Номер
24(26), С. 4766 - 4771
Опубликована: Июнь 27, 2022
Amide
synthesis
is
one
of
the
most
important
transformations
in
organic
chemistry
due
to
broad
application
pharmaceutical
drugs
and
materials.
In
this
report,
we
describe
a
mild
protocol
for
amide
formation
using
readily
available
nitroarenes
as
nitrogen
sources
an
inexpensive
iron
complex
catalyst.
Because
use
pH-neutral
conditions
avoidance
strong
oxidant
or
reductant,
wide
range
aromatic
aliphatic
aldehydes
well
with
various
functional
groups
could
be
tolerated
well.
A
plausible
mechanism
proposed
based
on
detailed
studies,
which
catalyst
initiates
radical
process
solvent
plays
key
role
O-atom
acceptor.
JACS Au,
Год журнала:
2021,
Номер
1(6), С. 742 - 749
Опубликована: Май 11, 2021
The
reduction
of
carboxylic
acids
to
the
respective
alcohols,
in
mild
conditions,
was
achieved
using
[MnBr(CO)5]
as
catalyst
and
bench
stable
PhSiH3
reducing
agent.
It
shown
that
reaction
with
earth-abundant
metal
could
be
performed
either
a
loading
low
0.5
mol
%,
rare
use
[MnBr(CO)5],
or
on
gram
scale
employing
only
1.5
equiv
PhSiH3,
lowest
amount
silane
reported
date
for
this
transformation.
Kinetic
data
control
experiments
have
provided
initial
insight
into
mechanism
catalytic
process,
suggesting
it
proceeds
via
formation
silyl
ester
intermediates
ligand
dissociation
generate
coordinatively
unsaturated
Mn(I)
complex
active
species.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(36)
Опубликована: Июнь 27, 2022
An
adaptive
catalytic
system
that
provides
control
over
the
nitroarene
hydrogenation
network
to
prepare
a
wide
range
of
aniline
and
hydroxylamine
derivatives
is
presented.
This
takes
advantage
delicate
interplay
between
rhodium(III)
center
Lewis
acidic
borane
introduced
in
secondary
coordination
sphere
metal.
The
high
chemoselectivity
catalyst
presence
various
potentially
vulnerable
functional
groups
its
readiness
be
deployed
at
preparative
scale
illustrate
practicality.
Mechanistic
studies
density
theory
(DFT)
methods
were
used
shed
light
on
mode
functioning
elucidate
origin
adaptivity.
competition
for
interaction
with
boron
solvent
molecule
substrate
was
found
crucial
When
operating
THF,
reduction
stops
platform,
whereas
reaction
can
directed
platform
toluene.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(35), С. 7036 - 7051
Опубликована: Янв. 1, 2023
This
review
provides
a
comprehensive
summary
of
the
utilization
ammonia
replacements
in
synthesizing
protected
and
free
primary
amines,
encompassing
both
traditional
reagents
latest
developments.
The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(24), С. 18067 - 18080
Опубликована: Ноя. 23, 2021
A
novel,
efficient,
and
atom-economical
approach
for
the
construction
of
quinazolinones
from
2-nitrobenzaldehydes
has
been
unveiled
via
copper-catalyzed
nitrile
formation,
hydrolysis,
reduction
in
one
pot
first
time.
In
this
reaction,
urea
is
used
as
a
source
nitrogen
hydrazine
hydrate
both
nitro
group
hydrolysis
nitrile,
atmospheric
oxygen
sole
oxidant.
The
method
portrays
wide
substrate
scope
with
good
functional
tolerances.
Moreover,
was
applied
synthesis
schizocommunin,
tryptanthrin,
phaitanthrin-A,
phaitanthrin-B,
8H-quinazolino[4,3-b]quinazolin-8-one.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(8)
Опубликована: Дек. 14, 2021
The
ability
to
selectively
react
one
functional
group
in
the
presence
of
another
underpins
efficient
reaction
sequences.
Despite
many
designer
catalytic
systems
being
reported
for
hydroboration
reactions,
which
allow
introduction
a
handle
cross-coupling
or
act
as
mild
method
reducing
polar
functionality,
these
platforms
rarely
deal
with
more
complex
where
multiple
potentially
reactive
sites
exist.
Here
we
demonstrate,
first
time,
use
light
distinguish
between
ketones
and
carboxylic
acids
molecules.
By
taking
advantage
different
activation
modes,
single
system
can
be
used
hydroboration,
chemoselectivity
dictated
only
by
absence
visible
light.