Angewandte Chemie,
Год журнала:
2024,
Номер
136(50)
Опубликована: Авг. 26, 2024
Abstract
We
report
a
strategy
for
the
formal
C−N
cross‐coupling
of
tertiary
amines
via
in
situ
generation
and
displacement
N‐acyl
ammonium
species.
Specifically,
treatment
diverse
with
TFAA
or
chloroformates
presence
NaI
leads
to
efficient
alkyl
iodides,
which
can
be
engaged
directly
Ni‐catalyzed
cross‐couplings.
The
protocol
is
applicable
acyclic
cyclic
systems,
including
highly
hindered
variants.
Applications
late‐stage
modification
complex
heterocycles
are
presented.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 10, 2025
The
cycloaddition
of
aziridines
with
unsaturated
compounds
is
a
valuable
method
for
synthesizing
nitrogen
heterocycles.
However,
this
process
predominantly
substrate-controlled,
posing
significant
challenges
in
regulating
the
regioselectivity
C–N
bond
cleavage.
In
study,
we
report
nickel-catalyzed
dynamic
kinetic
activation
strategy
that
enables
catalyst-controlled
aziridines.
Various
types
aziridines,
including
2-phenyl,
2-carbonyl,
2-alkyl,
and
disubstituted
consistently
cleave
their
more
sterically
hindered
bonds
to
generate
1,3-radical
anion
intermediates.
These
intermediates
participate
highly
regioselective
1,4-Heck/allylic
substitution
cascade
aromatic
branched
1,3-dienes,
resulting
radical-polar
crossover
(4
+
3)
produces
seven-membered
azepine
products.
This
approach
not
only
complements
traditional
dipolar
cycloaddition,
which
typically
act
as
zwitterionic
1,3-dipoles,
but
also
introduces
an
unusual
mode
1,3-dienes.
Experimental
investigations
density
functional
theory
(DFT)
calculations
provide
insight
into
reaction
mechanism.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(37), С. 25426 - 25432
Опубликована: Сен. 4, 2024
Herein,
we
report
the
first
example
of
a
highly
enantioselective
alkylative
aziridine
ring
opening.
Under
catalysis
chiral
nickel/pyridine-imidazoline
complex,
asymmetric
C(sp
The
transition-metal-catalyzed
ring-opening
functionalization
of
aziridines
presents
a
promising
approach
for
synthesizing
structurally
complex
amines.
However,
the
rearranged
poses
significant
challenges.
Herein,
we
report
first
alkenylation
with
aryl
alkenes
via
Ni-Brønsted
acid
co-catalysis,
leading
to
rapid
synthesis
diverse
array
allylamines
yields
reaching
up
91%.
Mechanistic
studies
suggest
that
reaction
occurs
through
rearrangement
aziridine
generate
an
imine
intermediate.
This
intermediate
is
subsequently
captured
by
alkene
under
nickel
catalysis,
ultimately
formation
allylamines.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(21), С. 14445 - 14452
Опубликована: Май 13, 2024
Transition-metal-catalyzed
C–Si/Ge
cross-coupling
offers
promising
avenues
for
the
synthesis
of
organosilanes/organogermanes,
yet
it
is
fraught
with
long-standing
challenges.
A
Ni/Ti-catalyzed
strategy
reported
here,
allowing
use
disubstituted
malononitriles
as
tertiary
C(sp3)
coupling
partners
to
couple
chlorosilanes
and
chlorogermanes,
respectively.
This
method
enables
catalytic
cleavage
C(sp3)–CN
bond
quaternary
carbon
followed
by
formation
C(sp3)–Si/C(sp3)–Ge
bonds
from
ubiquitously
available
starting
materials.
The
efficiency
generality
are
showcased
a
broad
scope
both
partners,
therefore
holding
potential
synthesize
structurally
diverse
organosilanes
organogermanes
that
were
difficult
access
previously.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 23, 2024
Cleavage
of
inert
C-N
bonds
in
unstrained
azacycles
such
as
pyrrolidine
remains
a
formidable
challenge
synthetic
chemistry.
To
address
this,
we
introduce
an
effective
strategy
for
the
reductive
cleavage
bond
Chemical Communications,
Год журнала:
2024,
Номер
60(17), С. 2405 - 2408
Опубликована: Янв. 1, 2024
Nickel-catalysed
chelation-assisted
reductive
cross-coupling
of
trifluoropropanamides/esters
with
disulfides
to
afford
thioacrylamides/esters
high
E
selectivity,
involving
triple
C–F
bond
cleavage.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Апрель 30, 2024
An
electrochemical
radical
Truce
Smiles
rearrangement
of
N-allylbenzamides
is
documented
herein.
The
selective
1,4-aryl
migration
was
triggered
by
the
fluoromethylation
alkene
providing
a
direct
route
to
fluoro
derivatives
highly
privileged
β-arylethylamine
pharmacophore.
This
practical
transformation
utilizes
readily
available
starting
materials
and
employs
an
electrical
current
drive
oxidative
process
under
mild
reaction
conditions.
It
accommodates
variety
migratory
aryl
groups
with
different
electronic
properties
substitution
patterns.
Careful
selection
protecting
group
on
nitrogen
atom
N-allylbenzamide
crucial
outcompete
undesired
6-endo
cyclization
achieve
high
level
selectivity
towards
migration.
DFT
calculations
support
mechanism
unveil
origin
between
two
competitive
pathways.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(31)
Опубликована: Май 3, 2024
β-Phenethylamines
are
widely
represented
in
biologically
and
pharmacologically
active
organic
small
molecules.
Here,
we
introduce
N-pyridinium
aziridines
as
latent
dual
electrophiles
for
the
synthesis
of
β-phenethylamines.
Bromide-promoted
ring
opening
generates
β-halopyridinium
amines.
Selective
Ni-catalyzed
C-C
cross-coupling
between
organozinc
nucleophiles
benzylic
C-Br
electrophile
affords
a
diverse
family
β-functionalized
phenethylaminopyridinium
salts,
coupling
is
stereoconvergent
presence
chiral
ligands.
Subsequent
reductive
N-N
bond
activation
within
salts
furnishes
products
formal
olefin
carboamination.
Other
cleavage
reactions
demonstrated
to
provide
access
free
primary
amines,
alkylated
heterocycles,
derived
from
N-centered
radical
chemistry.
The
developed
reaction
sequence
can
be
implemented
context
complex
molecules
natural
product
derivatives.
Together,
described
results
general
modular
β-phenethylamines
significantly
expand
utility
linchpins
chemical
synthesis.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(22), С. 6340 - 6346
Опубликована: Янв. 1, 2024
We
developed
the
first
transition-metal-catalyzed,
regiodivergent
sulfonylation
of
aziridines,
enabling
efficient
synthesis
diverse
β-amino
sulfones
under
mild
conditions
with
broad
substrate
compatibility
and
high
regioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
The
azidofunctionalization
of
alkenes
under
mild
conditions
using
commercially
available
starting
materials
and
easily
accessible
reagents
is
reported
based
on
a
radical-polar
crossover
strategy.
A
broad
range
alkenes,
including
vinyl
arenes,
enamides,
enol
ethers,
sulfides,
dehydroamino
esters,
were
regioselectively
functionalized
with
an
azide
nucleophiles
such
as
azoles,
carboxylic
acids,
alcohols,
phosphoric
oximes,
phenols.
method
led
to
more
efficient
synthesis
1,2-azidofunctionalized
pharmaceutical
intermediates
when
compared
previous
approaches,
resulting
in
both
reduction
step
count
increase
overall
yield.
scope
limitations
these
transformations
further
investigated
through
standard
unbiased
selection
15
substrate
combinations
out
1,175,658
possible
clustering
technique.
