Organic Letters,
Год журнала:
2022,
Номер
24(31), С. 5646 - 5650
Опубликована: Авг. 2, 2022
The
sturdy
chelation
of
1,2-diamines
and
transition-metals
would
retard
or
even
interrupt
the
routine
catalytic
cycles.
In
amidation
asymmetric
reductive
amination
(ARA)
cascade
reactions
diamines
ketoesters,
we
deployed
sets
additives
to
ensure
a
smooth
transformation
catalyzed
by
complexes
rhodium
versatile
highly
modular
phosphoramidite-phosphine
ligands.
tunability
ligands
was
fully
exploited
accommodate
various
α-ketoesters
for
efficient
synthesis
chiral
3,4-dihydroquinoxalinones.
Chemical Reviews,
Год журнала:
2023,
Номер
123(15), С. 9397 - 9446
Опубликована: Июль 7, 2023
The
proportion
of
approved
chiral
drugs
and
drug
candidates
under
medical
studies
has
surged
dramatically
over
the
past
two
decades.
As
a
consequence,
efficient
synthesis
enantiopure
pharmaceuticals
or
their
synthetic
intermediates
poses
profound
challenge
to
medicinal
process
chemists.
significant
advancement
in
asymmetric
catalysis
provided
an
effective
reliable
solution
this
challenge.
successful
application
transition
metal
catalysis,
organocatalysis,
biocatalysis
pharmaceutical
industries
promoted
discovery
by
precise
preparation
enantio-enriched
therapeutic
agents,
facilitated
industrial
production
active
ingredient
economic
environmentally
friendly
fashion.
present
review
summarizes
most
recent
applications
(2008–2022)
industry
ranging
from
scales
pilot
levels.
It
also
showcases
latest
achievements
trends
agents
with
state
art
technologies
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 9045 - 9062
Опубликована: Март 15, 2024
Methods
for
the
synthesis
of
α-branched
alkylamines
are
important
due
to
their
ubiquity
in
biologically
active
molecules.
Despite
development
many
methods
amine
preparation,
C(sp3)-rich
nitrogen-containing
compounds
continue
pose
challenges
synthesis.
While
carbonyl
reductive
amination
(CRA)
between
ketones
and
is
cornerstone
method
alkylamine
synthesis,
it
sometimes
limited
by
sterically
demanding
condensation
step
dialkyl
amines
more
restricted
availability
compared
aldehydes.
We
recently
reported
a
"higher-order"
variant
this
transformation,
alkylative
(CAA),
which
utilized
halogen
atom
transfer
(XAT)-mediated
radical
mechanism,
enabling
streamlined
complex
alkylamines.
efficacy
visible-light-driven
approach,
displayed
scalability
issues,
competitive
was
problem
certain
substrate
classes,
limiting
applicability.
Here,
we
report
change
reaction
regime
that
expands
CAA
platform
through
realization
an
extremely
broad
zinc-mediated
reaction.
This
new
strategy
enabled
elimination
CRA,
simplified
purification,
improved
scope.
Furthermore,
harnessed
carboxylic
acid
derivatives
as
alkyl
donors
facilitated
α-trialkyl
tertiary
amines,
cannot
be
accessed
via
CRA.
Zn-mediated
can
carried
out
at
variety
scales,
from
10
μmol
setup
microtiter
plates
high-throughput
experimentation,
gram-scale
medicinally-relevant
compounds.
believe
transformation
enables
robust,
efficient,
economical
access
provides
viable
alternative
current
benchmark
methods.
Chemical Science,
Год журнала:
2022,
Номер
13(17), С. 4697 - 4713
Опубликована: Янв. 1, 2022
IRED-catalyzed
reductive
aminations
have
progressed
from
mg
to
ton
scale,
through
advances
in
enzyme
discovery,
protein
engineering
and
process
biocatalysis.
Abstract
Direct
asymmetric
hydrogenation
(AH)
and
transfer
(ATH)
are
among
the
most
efficient
approaches
to
produce
chiral
building
blocks.
Recently,
these
types
of
transformations
have
witnessed
a
shift
towards
use
molecular
catalysts
based
on
earth‐abundant
transition
metals
due
their
ready
availability,
economic
advantage,
novel
properties.
With
particular
regard
manganese,
catalyst
development
has
seen
both
efficiency
substrate
scope
in
AH
ATH
greatly
improved,
with
emergence
large
number
well‐defined
Mn‐complexes
employed
this
field.
The
reaction
includes
C=O
bonds,
reduction
C=N
bonds
reductive
C=C
bonds.
Herein,
our
survey
area
focuses
catalytic
activity
such
complexes,
versatility
routes
convert
substrates
target
molecules.
We
consider
collected
findings
article
will
be
helpful
reader
by
providing
an
insight
into
ligand
design,
thereby
aiding
future
development.
Moreover,
review
is
aimed
at
highlighting
remarkable
progress
made
last
seven
years
manganese
complexes
for
enantioselective
reduction.
Green Chemistry,
Год журнала:
2022,
Номер
24(16), С. 6172 - 6178
Опубликована: Янв. 1, 2022
Surfactant-enabled
asymmetric
ATA-catalyzed
reductive
aminations
in
aqueous
buffered
media
are
described,
representative
of
the
enhanced
levels
conversion
made
possible
by
presence
a
nonionic
surfactant
water,
thereby
enabling
1-pot
chemoenzymatic
catalysis.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(7)
Опубликована: Фев. 17, 2022
Abstract
It
is
only
in
the
two
last
decades
that
first
examples
of
organocatalytic
dynamic
kinetic
resolutions
(DKRs)
have
been
disclosed.
These
methodologies
allow
resolving
racemic
compounds
with
up
to
quantitative
yield.
Today,
a
variety
chiral
organocatalysts
are
capable
providing
excellent
enantioselectivities
many
types
transformations
evolving
through
DKR.
The
goal
this
review
update
field
DKRs
since
2016.
divided
into
six
sections,
according
different
employed
these
reactions,
such
as
Brønsted
acid
catalysts,
hydrogen‐bonding
N‐heterocyclic
carbene
Lewis
base
phase‐transfer
and
cinchona
alkaloid‐based
catalysts.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(29)
Опубликована: Май 7, 2022
Abstract
A
Pd‐catalyzed
asymmetric
double
hydroxycarbonylation
of
terminal
alkynes
was
developed
by
using
relay
catalysis,
providing
a
highly
efficient
route
to
chiral
succinic
acids
(41
examples,
76–94
%,
94–99
%
ee
).
Key
success
the
combinatorial
use
Pd
precursor
with
two
distinct
phosphine
ligands
in
one
pot.
The
synthetic
utilities
this
protocol
were
showcased
facile
synthesis
key
intermediates
for
pharmaceuticals.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 17, 2024
This
perspective
details
advances
made
in
the
field
of
Ni-catalyzed
C–N
bond
formation.
The
use
this
Earth
abundant
metal
to
decorate
amines,
amides,
lactams,
and
heterocycles
enables
direct
access
a
variety
biologically
active
industrially
relevant
compounds
sustainable
manner.
Herein,
different
strategies
that
leverage
propensity
Ni
facilitate
both
one-
two-electron
processes
will
be
surveyed.
first
part
Perspective
focuses
on
couplings
at
room
temperature
by
accessing
oxidized
Ni(III)
intermediates.
In
context,
photochemical,
electrochemical,
chemically
mediated
analyzed.
A
special
emphasis
has
been
put
providing
comprehensive
explanation
mechanistic
avenues
have
proposed
these
chemistries;
either
Ni(I/III)
self-sustained
cycles
or
Ni(0/II/III)
photochemically
pathways.
second
ligand
designs
also
enable
reactivity
via
Ni(0/II)
mechanism.
Finally,
we
discuss
our
thoughts
possible
future
directions
field.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Июнь 10, 2022
Abstract
Direct
asymmetric
reductive
amination
is
one
of
the
most
efficient
methods
for
construction
chiral
amines,
in
which
scope
applicable
amine
coupling
partners
remains
a
significant
challenge.
In
this
study
we
describe
primary
alkyl
amines
effectively
serve
as
N-sources
direct
catalyzed
by
iridium
precursor
and
sterically
tunable
phosphoramidite
ligands.
The
density
functional
theory
studies
reaction
mechanism
imply
substrates
ligand
strengthened
(N)H-O(P)
hydrogen-bonding
attraction,
hydride
addition
occurs
via
an
outer-sphere
transition
state,
Cl-H
H-bonding
plays
important
role.
Through
concise
procedure,
cinacalcet,
tecalcet,
fendiline
many
other
related
have
been
synthesized
single
step
with
high
yields
excellent
enantioselectivity.
