Molecules,
Год журнала:
2024,
Номер
29(21), С. 5090 - 5090
Опубликована: Окт. 28, 2024
Carbon–carbon
bond
formation
represents
a
key
reaction
in
organic
synthesis,
resulting
paramount
importance
for
constructing
the
carbon
backbone
of
molecules.
However,
traditional
metal-based
catalysis,
despite
its
advantages,
often
struggles
with
issues
related
to
efficiency,
selectivity,
and
sustainability.
On
other
hand,
while
biocatalysis
offers
superior
selectivity
due
an
extraordinary
recognition
process
substrate,
scope
applicable
reactions
remains
somewhat
limited.
In
this
context,
Artificial
Metalloenzymes
(ArMs)
Metallo
Peptides
(MPs)
offer
promising
not
fully
explored
solution,
merging
two
fields
transition
metal
catalysis
biotransformations,
by
inserting
catalytically
active
cofactor
into
customizable
protein
scaffold
or
coordinating
ion
directly
short
tunable
amino
acid
(Aa)
sequence,
respectively.
As
result,
these
hybrid
catalysts
have
gained
attention
as
valuable
tools
challenging
catalytic
transformations,
providing
systems
new-to-nature
properties
synthesis.
This
review
overview
recent
advances
development
ArMs
MPs,
focusing
on
their
application
asymmetric
carbon–carbon
bond-forming
reactions,
such
carbene
insertion,
Michael
additions,
Friedel–Crafts
cross-coupling
cyclopropanation,
underscoring
versatility
synthesizing
biologically
relevant
compounds.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12318 - 12325
Опубликована: Авг. 15, 2024
Chiral
manganese(I)
complexes
that
contain
carbocyclic-fused
8-amino-5,6,7,8-tetrahydroquinolinyl
groups
are
appended
with
distinct
para-R
substituents
have
proven
to
be
effective
catalysts
in
the
asymmetric
transfer
hydrogenation
(ATH)
of
a
wide
range
ketones
(48
examples).
Notably,
Mn2
proved
most
productive
catalyst,
allowing
an
outstanding
turnover
number
8300
catalyst
loadings
as
low
0.01
mol
%.
Furthermore,
this
catalytic
protocol
shows
considerable
promise
for
applications
synthesis
chiral
drugs
such
Lusutrombopag.
The
asymmetric
hydrogenation
(AH)
of
cyclic
N-alkyl
imines
offers
an
elegant
and
efficient
method
to
afford
chiral
amines,
especially
for
S-nicotine
its
derivatives.
However,
this
approach
remains
ongoing
challenge
due
undesirable
coordination
pyridyl-containing
substrates
the
active
metal
catalyst.
Herein,
we
disclose
a
manganese-catalyzed
AH
that
allows
access
other
α-(hetero)aryl
pyrrolidines
provides
example
base-metal
catalyst
displays
superior
performance
noble
counterparts.
A
highly
enantioselective
Mn-catalyzed
hydrogenation
of
fluorinated
imines
has
been
realized.
The
success
this
is
attributed
to
the
use
chiral
ferrocenyl
P,N,N
ligand
bearing
an
additional
center
at
pyridinylmethyl
position.
displayed
broad
functional
group
tolerance,
thus
furnishing
a
wide
range
optically
active
amines
with
up
98%
enantiomeric
excess.
utility
methodology
well-demonstrated
by
scale-up
asymmetric
N-(4′-methoxyphenyl)-ethan-2,2,2-trifluoro-1-phenyl-1-imine.
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 17633 - 17641
Опубликована: Ноя. 15, 2024
An
atroposelective
dynamic
kinetic
resolution
of
configurationally
labile
heterobiaryl
ketone
N-oxides
via
Mn-catalyzed
asymmetric
hydrogenation
has
been
disclosed.
By
use
a
structurally
finely
tuned
chiral
ferrocenyl
P,N,N-ligand,
the
proceeds
smoothly
under
mild
conditions
with
simultaneous
installation
central
and
axial
chirality,
giving
wide
range
atropisomeric
1-arylisoquinoline
2-arylpyridine
bearing
alcohol
structure
high
diastereo-
enantioselectivities.
The
diastereomer
product
could
be
readily
prepared
in
stereospecific
way
complete
inversion
chirality
Mitsunobu
reaction.
value
this
central-
axial-chiral
N-oxide
scaffold
is
preliminarily
demonstrated
by
its
successful
utility
as
catalyst
allylation
benzaldehyde
allyltrichlorosilane.
Abstract
This
review
of
reviews
attempts
to
systematically
analyze
the
recent
advancements
in
transition
metal‐catalyzed
hydrogenation
reactions
as
discussed
previous
articles,
emphasizing
computational
insights
that
enhance
our
understanding
reaction
mechanisms.
It
highlights
efficacy
density
functional
theory
(DFT)
calculating
free
energies,
exploring
mechanistic
pathways
and
kinetics
processes
and,
focusing
on
substrates
such
alkenes,
alkynes,
amides,
imines,
nitriles,
carbon
dioxide.
The
details
significant
studies
where
models
help
predict
outcomes
aid
catalyst
design.
Notable
discussions
include
role
solvent
effects
metal‐ligand
interactions,
which
are
crucial
for
reactivity
selectivity
but
often
underestimated
models.
concludes
with
current
challenges
prospects,
suggesting
enhanced
experimental
collaborations
refine
