Abstract
N-Arylpiperazines
are
prominent
structures
found
in
natural
products
and
synthetic
chemical
entities,
including
therapeutic
agents.
In
this
work,
we
introduce
a
novel
strategy
for
the
effective
synthesis
of
distinctive
piperazine
compounds
through
post-Ugi
cyclization
under
transition-metal-free
conditions.
This
method
involves
formation
four-component
Ugi
adduct
by
combining
an
aldehyde,
isocyanide,
primary
propargylamine,
oxamic
acid.
Subsequently,
intramolecular
alkyne
hydroamination
reaction
occurs,
leading
to
derivative
carbon–nitrogen
bond
formation.
The
have
been
characterized
1H
13C
NMR
spectroscopy.
Science,
Год журнала:
2024,
Номер
383(6678), С. 77 - 81
Опубликована: Янв. 4, 2024
Catalytic
methods
to
couple
alkene
and
amine
feedstocks
are
valuable
in
synthetic
chemistry.
The
direct
carbonylative
coupling
of
alkenes
amines
holds
promise
as
a
perfectly
atom-economical
approach
amide
synthesis,
but
general
remain
underdeveloped.
Herein,
we
report
an
hydroaminocarbonylation
catalyzed
by
unmodified,
inexpensive
cobalt
carbonyl
under
mild
conditions
low
pressure
promoted
light.
Silane
addition
after
the
reaction
enables
sequential
cobalt-catalyzed
reduction,
constituting
formal
hydroaminomethylation.
These
exhibit
exceptional
scope
across
both
components
with
high
chemo-
regioselectivity
proceed
efficiently
even
absence
solvent.
formation
hydridocobalt
through
photodissociation
ligand
is
proposed
enable
catalytic
activity
conditions,
which
addresses
long-standing
challenge
catalysis.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
The
direct
synthesis
of
C(sp3)-rich
architectures
is
a
driving
force
for
innovation
in
synthetic
organic
chemistry.
Such
scaffolds
impart
beneficial
properties
onto
drug
molecules
that
correlate
with
greater
clinical
success.
Consequently,
there
strong
impetus
to
develop
new
methods
by
which
access
sp3-rich
from
commercial
feedstocks,
such
as
alkenes.
Herein,
we
report
three-component
aminoalkylation
reaction
utilizes
the
principles
triple
radical
sorting
regioselectively
add
N-centered
and
C-centered
radicals
across
This
process
relies
upon
photoredox
catalysis
transform
alkyl
bromides
reductively
activated
precursors
into
high-energy
species
redox-neutral
fashion.
A
broad
scope
coupling
partners
demonstrated,
multiple
applications,
including
facile
syntheses
pharmacophoric
substituted
N-heterocycles.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
Herein,
we
introduce
a
Ni-catalyzed
asymmetric
homobenzylic
hydroamidation
reaction
that
efficiently
addresses
the
dual
challenges
of
achieving
regio-
and
enantioselectivity
in
synthesis
β-(hetero)arylethylamides.
By
employing
transposed
NiH
catalysis
approach,
this
method
facilitates
formation
key
chiral
nickel-amido
intermediates,
enabling
insertion
into
alkenes
to
produce
desired
β-arylamide
products
with
excellent
enantioselectivity.
The
exhibits
high
functional
group
tolerance
utilizes
readily
available
starting
materials
vinylarenes
react
dioxazolone
as
robust
amidating
source.
Notably,
approach
was
successfully
applied
pharmaceutical
compounds
natural
products,
such
Clobenzorex,
Direx,
Selegiline,
Sacubitril,
Cipargamin.
Chemical Communications,
Год журнала:
2024,
Номер
60(50), С. 6340 - 6361
Опубликована: Янв. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2762 - 2767
Опубликована: Янв. 1, 2024
A
P(NMe2)3-catalyzed
[4
+
2]
annulation
of
2-amino-β-nitrostyrenes
and
β′-acetoxy
allenoates
followed
by
a
Zn/AcOH-mediated
reduction–hydroamination–isomerization
has
been
developed.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(40), С. 21738 - 21744
Опубликована: Окт. 3, 2023
We
report
a
light-driven
method
for
the
intermolecular
anti-Markovnikov
hydroamination
of
alkenes
with
primary
heteroaryl
amines.
In
this
protocol,
electron
transfer
between
an
amine
substrate
and
excited-state
iridium
photocatalyst
affords
aminium
radical
cation
(ARC)
intermediate
that
undergoes
C–N
bond
formation
nucleophilic
alkene.
Integral
to
reaction
success
is
electronic
character
amine,
wherein
increasingly
electron-deficient
amines
generate
reactive
ARCs.
Counteranion-dependent
reactivity
observed,
triflate
photocatalysts
are
employed
in
place
conventional
hexafluorophosphate
complexes.
This
exhibits
broad
functional
group
tolerance
across
55
examples
N-alkylated
products
derived
from
pharmaceutically
relevant
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(13), С. 1827 - 1838
Опубликована: Июнь 21, 2024
ConspectusChemists
have
long
been
inspired
by
biological
photosynthesis,
wherein
a
series
of
excited-state
electron
transfer
(ET)
events
facilitate
the
conversion
low
energy
starting
materials
such
as
H
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 20, 2025
Due
to
their
conductive
properties
and
optoelectronic
tunability,
MXenes
have
revolutionized
the
area
of
electrocatalysis
active
materials
in
supercapacitors.
In
comparison,
there
are
only
a
few
reports
on
as
thermal
catalysts
for
general
organic
reactions.
Herein,
unprecedented
catalytic
activity
Ti3C2
MXene
hydroamination
alkynes
is
reported,
overcoming
limitations
poor
activity,
lack
selectivity,
stability,
which
generally
encountered
solid
known
so
far.
case
Ti3C2,
exhibits
almost
complete
selectivity
anti-Markovnikov
regioisomer,
both
aliphatic
amines
less-reactive
aromatic
amines.
also
efficiently
catalyzes
intramolecular
hydroamination,
leading
formation
indol
heterocycles.
The
C-C
multiple
bonds
reaction
with
atom
efficiency
that
may
form
C-N
from
convenient
reagents.
maximum
number
sites
nanosheets
quantified
by
thermoprogrammed
NH3
desorption.
measured
TOF
values
order
102
h-1,
highest
value
being
350
h-1
1-hexyne
n-butylamine.
Therefore,
among
heterogeneous
studied,
its
per
site
comparable
best
reported
Density
functional
theory
calculations
models
indicate
cooperation
neighboring
Ti
atoms
mechanism.
Considering
compositional
structural
versatility
MXenes,
present
findings
open
door
further
application
other
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(41)
Опубликована: Авг. 23, 2023
An
iridium-catalyzed
remote
site-switchable
hydroarylation
of
alkenes
was
reported,
delivering
the
products
functionalized
at
subterminal
methylene
and
terminal
methyl
positions
on
an
alkyl
chain
controlled
by
two
different
ligands,
respectively,
in
good
yields
with
to
excellent
site-selectivities.
The
catalytic
system
showed
functional
group
tolerance
a
broad
substrate
scope,
including
unactivated
activated
alkenes.
More
importantly,
regioconvergent
transformations
mixtures
isomeric
were
also
successfully
realized.
results
mechanistic
studies
demonstrate
that
reaction
undergoes
chain-walking
process
give
[Ar-Ir-H]
complex
alkene.
subsequent
processes
proceed
through
modified
Chalk-Harrod-type
mechanism
via
migratory
insertion
alkene
into
Ir-C
bond
followed
C-H
reductive
elimination
afford
hydrofunctionalization
site-selectively.
