Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27307 - 27311
Опубликована: Окт. 26, 2021
Abstract
Asymmetric
reductive
amination
(ARA)
is
one
of
the
most
promising
methods
for
synthesis
chiral
amines.
Herein
we
report
our
efforts
on
merging
two
ARA
reactions
into
a
single‐step
transformation.
Catalyzed
by
complex
formed
from
iridium
and
steric
hindered
phosphoramidite,
readily
available
inexpensive
aromatic
ketones
initially
undergo
first
with
ammonium
acetate
to
afford
primary
amines,
which
serve
as
amine
sources
second
ARA,
finally
provide
enantiopure
C
2
‐symmetric
secondary
products.
The
developed
process
competently
enables
successive
coupling
inorganic
organic
nitrogen
in
same
reaction
system.
Brønsted
acid
additive
plays
multiple
roles
this
procedure:
it
accelerates
formation
imine
intermediates,
minimizes
inhibitory
effect
N‐containing
species
catalyst,
reduces
side
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(15)
Опубликована: Фев. 14, 2023
Abstract
Reductive
amination
is
a
valuable
method
for
amine
synthesis
that
has
been
the
topic
of
century‘s
worth
in‐depth
study
in
both
academia
and
industry.
Amines
their
derivatives
serve
as
incredibly
adaptable
building
blocks
broad
array
organic
substrates
are
significant
precursors
myriad
advanced
chemicals,
physiologically
active
compounds,
agrochemicals,
biomolecules,
pharmaceuticals,
polymers.
The
creation
innovative
catalytic
processes
long‐term
selective
amines
from
readily
accessible
environmentally
benign
reagents
remains
top
priority
chemical
research.
Both
heterogeneous
homogeneous
catalysts
have
designed
with
success
to
enable
these
reactions
explore
new
amines.
Ruthenium
employed
reductive
owing
stability,
selectivity,
versatility,
low
toxicity,
high
efficiency.
This
review
comprehensively
overviews
Ru‐catalyzed
includes
literature
2009
2022.
This
report
describes
a
new
kinetic
resolution-asymmetric
reductive
amination
strategy
to
collectively
gain
access
both
primary
and
secondary
chiral
NH-unprotected
amines.
Catalyzed
by
the
complex
of
iridium
bulky
tunable
phosphoramidite
ligands,
various
ketones
racemic
amines
could
be
smoothly
converted
two
different
types
amine
products.
Bronsted
acids
as
additives
play
triple
roles,
decreasing
inhibitory
effect,
promoting
formation
imine
intermediates,
guiding
reaction
proceed
through
"outer-sphere"
H-addition
along
with
ligand.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27307 - 27311
Опубликована: Окт. 26, 2021
Abstract
Asymmetric
reductive
amination
(ARA)
is
one
of
the
most
promising
methods
for
synthesis
chiral
amines.
Herein
we
report
our
efforts
on
merging
two
ARA
reactions
into
a
single‐step
transformation.
Catalyzed
by
complex
formed
from
iridium
and
steric
hindered
phosphoramidite,
readily
available
inexpensive
aromatic
ketones
initially
undergo
first
with
ammonium
acetate
to
afford
primary
amines,
which
serve
as
amine
sources
second
ARA,
finally
provide
enantiopure
C
2
‐symmetric
secondary
products.
The
developed
process
competently
enables
successive
coupling
inorganic
organic
nitrogen
in
same
reaction
system.
Brønsted
acid
additive
plays
multiple
roles
this
procedure:
it
accelerates
formation
imine
intermediates,
minimizes
inhibitory
effect
N‐containing
species
catalyst,
reduces
side
