The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8656 - 8667
Опубликована: Июнь 4, 2024
The
nucleophilic
ring-opening
of
aziridine
derivatives
provides
an
important
synthetic
tool
for
the
preparation
various
β-functionalized
amines.
Amines
as
nucleophiles
are
employed
to
prepare
synthetically
useful
1,2-diamines
in
presence
catalysts
or
activators.
Herein,
B2(OH)4-mediated
reductive
transformation
N-tosyl
aziridines
by
nitroarenes
was
developed.
This
aqueous
protocol
cheap
and
readily
available
amino
sources
proceeds
under
external
catalyst-free
conditions.
Control
experiments
DFT
calculations
pointed
situ
reduction
aryl
amines
via
N-aryl
boramidic
acid
(E)
SN1-type
N-tosylaziridines
resultant
with
high
regioselectivity.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(14), С. 10316 - 10326
Опубликована: Июль 1, 2024
Electron-rich
diarylamines,
exemplified
by
anisole-derived
amines,
play
pivotal
roles
in
process
chemistry,
pharmaceuticals,
and
materials.
In
this
study,
homo-diarylamines
were
synthesized
directly
from
the
C-H
activation
of
electron-rich
arenes
sodium
nitrate/trifluoroacetic
acid
successive
treatment
iron
powder.
Mechanistic
investigations
reveal
that
nitrosoarene
serves
as
reaction
intermediate,
formation
second
C-N
bond
between
resulting
arene
is
catalyzed
nitrosonium
ion
(NO
Abstract
Anilines
are
a
common
motif
in
many
bioactive
compounds
and
their
production
through
the
reduction
of
nitroarenes
has
become
an
essential
method
for
synthesis.
We
demonstrate
that
combination
amine-borane
complex
hypoboric
acid
(tetrahydroxydiborane)
under
visible
light
irradiation
can
accomplish
to
corresponding
anilines.
Preliminary
mechanistic
studies
suggest
generation
boryl
radicals
via
hydrogen
atom
transfer
(HAT)
step
from
photoexcited
nitroarene.
Involvement
parallel
thermal
pathway
is
demonstrated
with
high
reaction
efficiency
being
partially
attributed
both
routes.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8656 - 8667
Опубликована: Июнь 4, 2024
The
nucleophilic
ring-opening
of
aziridine
derivatives
provides
an
important
synthetic
tool
for
the
preparation
various
β-functionalized
amines.
Amines
as
nucleophiles
are
employed
to
prepare
synthetically
useful
1,2-diamines
in
presence
catalysts
or
activators.
Herein,
B2(OH)4-mediated
reductive
transformation
N-tosyl
aziridines
by
nitroarenes
was
developed.
This
aqueous
protocol
cheap
and
readily
available
amino
sources
proceeds
under
external
catalyst-free
conditions.
Control
experiments
DFT
calculations
pointed
situ
reduction
aryl
amines
via
N-aryl
boramidic
acid
(E)
SN1-type
N-tosylaziridines
resultant
with
high
regioselectivity.
