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.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(40), С. 8102 - 8108
Опубликована: Янв. 1, 2024
A
practical
electrochemical
sulfonylation-triggered
Truce–Smiles
rearrangement
of
N
-allylbenzamides
yielded
sulfone-
and
sulfonic
acid-containing
β-arylethylamines
under
mild
oxidant-free
reaction
conditions.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(21), С. 15822 - 15833
Опубликована: Окт. 18, 2024
Herein,
we
report
a
general
and
efficient
Ni-catalyzed
reductive
cross-coupling
reaction
of
substituted
vinyl
bromides
α-chloro
phosphonates
to
access
set
α-vinyl
using
zinc
as
the
terminal
reductant.
This
exhibits
broad
substrate
adaptability
good
functional
group
tolerance,
which
allows
afford
diverse
compounds
including
structurally
complex
motifs
from
natural
products
drugs.
Furthermore,
practicality
was
certificated
through
gram-scale
transformation
experiments.
The
preliminary
mechanistic
investigations
support
radical
chain
process.
potential
realize
enantiomeric
control
makes
it
more
valuable
for
further
exploration.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(12)
Опубликована: Янв. 25, 2024
Abstract
This
manuscript
describes
the
development
of
alkyne
addition
to
aziridine
moiety
aziridinoquinoxalines
using
dual
Ir(III)/Cu(I)
catalytic
system
under
green
light‐emitting
diode
(LED)
photolysis
(λ
max
=525
nm).
mild
method
features
high
levels
chemo‐
and
regioselectivity
was
used
generate
30
highly
functionalized
substituted
dihydroquinoxalines
in
36–98
%
yield.
transformation
also
carried
asymmetrically
phthalazinamine‐based
chiral
ligand
provide
9
products
96
:
4
86
14
e.r.
The
experimental
quantum
chemical
explorations
this
reaction
suggest
a
mechanism
that
involves
Ir(III)‐catalyzed
triplet
energy
transfer
followed
by
ring‐opening
ultimately
leading
formation
azomethine
ylide
intermediates.
These
intermediates
undergo
sequential
protonation/copper(I)
acetylide
products.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(29)
Опубликована: Апрель 30, 2024
Abstract
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,
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.
