Abstract
The
catalytic
three‐component
radical
carboamination
of
alkenes
has
recently
emerged
as
an
alternative
and
robust
platform
for
the
rapid
construction
diverse
valuable
amines.
Despite
great
advances
in
this
field,
new
methods
that
enable
highly
selective
access
to
chemical
space
surrounding
amine
functional
groups
are
still
high
demand.
Herein,
we
report
a
generally
applicable
visible
light‐induced
copper‐catalyzed
cyanoalkylamination
reaction
alkenes,
oxime
carbonates,
benzoyloxycarbamates.
This
protocol
demonstrates
chemo‐selectivity,
broad
substrate
scope,
good
group
tolerance,
providing
variety
cyanoalkylated
aliphatic
amines
with
yields.
Chemical Communications,
Год журнала:
2024,
Номер
60(68), С. 8946 - 8977
Опубликована: Янв. 1, 2024
Alkene
carbofunctionalization
reactions
have
great
potential
for
synthesizing
complex
molecules
and
constructing
structures
in
natural
products
medicinal
chemistry.
Recently,
dual
photoredox/nickel
catalysis
has
emerged
as
a
novel
strategy
alkene
carbofunctionalization.
Nickel
offers
numerous
advantages
over
other
transition
metals,
such
cost-effectiveness,
abundance,
low
toxicity,
moreover,
it
many
oxidation
states.
catalysts
exhibit
excellent
catalytic
activity
photoredox/transition
metal
catalysis,
facilitating
the
formation
of
carbon-carbon
or
carbon-heteroatom
bonds
organic
transformations.
This
review
highlights
latest
advancements
photoredox/nickel-catalyzed
carbofunctionalizations
includes
literature
published
from
2020
to
2024.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
silver-catalyzed
cross
coupling
of
cyclic
aldimines
and
α-imino-oxy
acids
has
been
developed.
The
solvent-dependent
reaction
could
selectively
deliver
either
imine
moiety
retained
nitriles
or
ring-opened
oxonitriles
in
moderate
yields.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 24, 2025
In
view
of
the
frequent
occurrence
carbon-nitrogen
bonds
in
organic
compounds,
development
powerful
new
methods
for
construction
such
is
expected
to
greatly
impact
many
fields
that
utilize
molecules.
While
substitution
an
alkyl
electrophile
by
a
nitrogen
nucleophile
seemingly
straightforward
approach
generating
bond,
practice
classical
pathways
have
very
substantial
limitations
case
unactivated
secondary
and
tertiary
electrophiles.
Recent
reports
transition
metals
can
catalyze
certain
reactions
electrophiles
are
therefore
considerable
significance;
however,
virtually
no
been
developed
wherein
absolute
stereochemistry
controlled
together
with
bond
formation.
Herein,
we
address
this
dual
challenge
reactivity
enantioselectivity,
describing
photoinduced,
copper-catalyzed
enantioconvergent
synthesis
β-aminoalcohol
derivatives
via
coupling
anilines
racemic,
β-haloethers.
We
apply
method
catalytic
asymmetric
metolachlor,
report
array
mechanistic
studies
consistent
reaction
pathway
propose.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(67)
Опубликована: Авг. 13, 2024
Abstract
Difunctionalizations
of
alkenes
represent
one
the
most
straightforward
protocols
to
build
molecular
complexity
due
simultaneous
construction
two
vicinal
bonds
cross
π‐bond
alkenes.
It
is
extremely
attractive
yet
challenging
control
stereochemistry
outcome
this
event.
Over
past
years,
visible‐light
and
Ni‐catalyzed
asymmetric
difunctionalizations
provide
an
environmental
benign
promising
solution
for
saturated
carbon
centers
with
regio‐
enantioselectivity.
In
Concept,
initiative
progress
enantioselective
enabled
by
nickel
catalysis
has
been
summarized.
Moreover,
further
efforts
directions
development
mediated
discussed.
Abstract
Allylic
amide
moieties
are
commonly
encountered
in
natural
products
and
privileged
structures
pharmaceuticals
agrochemicals.
Moreover,
because
allylic
can
be
to
converted
into
an
array
of
high‐value
motifs,
they
have
been
widely
employed
organic
synthesis.
However,
the
development
catalytic
systems
for
intermolecular
amidation
olefins,
particularly
branched
α
‐olefins,
has
proven
challenging.
Here,
a
biomimetic,
synergistic
method
is
reported
that
combines
photoredox,
cobalt,
Brønsted
base
catalysis
synthesis
substituted
amides
from
‐olefins
simple
imides
without
using
oxidants.
This
low‐cost,
operationally
features
broad
substrate
scope
excellent
functional
group
compatibility.
it
successfully
used
functionalization
several
structurally
complex
molecules
demonstrating
method's
potential
utility
medicinal
chemistry
applications.
Mechanistic
studies
revealed
C(
sp
3
)─N
bond
formation
mediated
by
nitrogen‐centered
radical
intermediate,
which
generated
via
sequence
involving
deprotonation
single‐electron
oxidation.
Herein,
we
report
a
visible-light-driven
and
cobalt-mediated
1,4-hydroamination
reaction
of
1,3-dienes
with
arylmines
as
the
nucleophiles.
The
involves
regioselective
addition
[CoIII]–H
to
1,3-diene,
followed
by
oxidation
nucleophilic
substitution
amines.
Using
Ir(ppy)3
photocatalyst
enables
cobalt
redox
cycle
be
implemented
without
using
an
external
oxidant
hydride
regent.
This
protocol
can
applied
well
forge
carbon–oxygen
carbon–sulfur
bonds
in
analogous
way.
We
report
a
novel
coupling
strategy
enabled
by
cyclic
diphenylchloronium
salt
that
facilitates
reactions
between
sulfides
and
diverse
nucleophiles,
including
oxygen-
nitrogen-based
species.
The
methodology
efficiently
produces
structurally
varied
valuable
compounds,
carbamates,
carboxylic
esters,
aryl
ethers,
alkylated
amines,
under
mild,
operationally
simple
conditions.
protocol's
synthetic
utility
was
highlighted
through
modular
preparation
of
five
important
drugs
structural
analogues,
demonstrating
significant
potential
for
drug
discovery
applications.
