Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
Understanding
the
nature
of
a
transition-metal-catalyzed
process,
including
catalyst
evolution
and
real
active
species,
is
rather
challenging
yet
great
importance
for
rational
design
development
novel
catalysts,
this
even
more
difficult
bimetallic
catalytic
system.
Pd(0)/carboxylic
acid
combined
system-catalyzed
allylic
alkylation
reaction
alkynes
has
been
used
as
an
atom-economical
protocol
synthesis
products.
However,
asymmetric
version
still
limited,
in-depth
understanding
Pd
species
elusive.
Herein
we
report
enantioselective
coupling
between
readily
available
aldimine
esters
using
synergistic
Cu/Pd
system,
affording
diverse
set
α-quaternary
allyl
amino
ester
derivatives
in
good
yields
with
excellent
enantioselectivities.
Mechanistic
studies
indicated
that
it
most
likely
molecular
Cu
catalysis
nanoparticle
catalysis.
The
precursor
transformed
to
soluble
nanoparticles
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(15), С. 4996 - 5012
Опубликована: Янв. 1, 2023
This
review
summarises
the
state-of-the-art
in
transition-metal
catalysed
asymmetric
hydrogenation
of
(hetero)arenes
and
highlights
recent
advances
with
a
special
focus
on
sustainability
while
also
addressing
its
shortcomings.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(9), С. 5864 - 5871
Опубликована: Фев. 20, 2024
Sulfur,
alongside
oxygen
and
nitrogen,
holds
a
prominent
position
as
one
of
the
key
heteroatoms
in
nature
medicinal
chemistry.
Its
significance
stems
from
its
ability
to
adopt
different
oxidation
states,
rendering
it
valuable
both
polarity
handle
hydrogen
bond
donor/acceptor.
Nevertheless,
poisonous
free
electron
pairs
makes
sulfur
containing
substrates
inaccessible
for
many
catalytic
protocols.
Strong
(at
low
temperatures)
irreversible
chemisorption
catalyst's
surface
is
particular
detrimental
heterogeneous
catalysts,
possessing
only
few
catalytically
active
sites.
Herein,
we
present
novel
Ru-S
catalyst
that
tolerates
multiple
functionalities,
including
thioethers,
thiophenes,
sulfoxides,
sulfones,
sulfonamides,
sulfoximines,
hydrogenation
quinolines.
The
utility
products
was
further
demonstrated
by
subsequent
diversifications
functionalities.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 29, 2025
Due
to
their
strong
aromaticity
and
difficulties
in
chemo-,
regio-,
enantioselectivity
control,
asymmetric
hydrogenation
of
naphthol
derivatives
1,2,3,4-tetrahydronaphthols
has
remained
a
long-standing
challenge.
Herein,
we
report
the
first
example
homogeneous
catalyzed
by
tethered
rhodium-diamine
catalysts,
affording
wide
array
optically
pure
high
yields
with
excellent
enantioselectivities
(up
98%
yield
>99%
ee).
Mechanistic
studies
experimental
computational
approaches
reveal
that
fluorinated
solvent
1,1,1,3,3,3-hexafluoroisopropanol
(HFIP)
plays
vital
roles
control
reactivity
selectivity,
1-naphthol
is
reduced
via
cascade
reaction
pathway,
including
dearomative
tautomerization,
1,4-hydride
addition,
1,2-hydride
addition
sequence.
A
novel
synergistic
activation
mode
was
proposed
which
HFIP
assists
both
hydrogen
molecule
presence
base,
situ-generated
fleeting
keto
tautomer
immediately
trapped
Rh(III)-H
species
before
it
escapes
from
cage.
This
protocol
provides
straightforward
practical
pathway
for
synthesis
key
intermediates
several
chiral
drugs.
Particularly,
Nadolol,
drug
treatment
hypertension,
angina
pectoris,
congestive
heart
failure,
certain
arrhythmias,
enantioselectively
synthesized
time.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 4109 - 4118
Опубликована: Фев. 13, 2023
A
catalytic
approach
of
synthesizing
the
cis-selective
saturated
carbo-
and
heterocyclic
germanium
compounds
(3D
framework)
is
reported
via
hydrogenation
readily
accessible
aromatic
germanes
(2D
framework).
Among
numerous
catalysts
tested,
Nishimura's
catalyst
(Rh2O3/PtO2·H2O)
exhibited
best
reactivity
with
an
isolated
yield
up
to
96%.
broad
range
substrates
including
synthesis
unprecedented
was
explored.
This
selective
strategy
could
tolerate
several
functional
groups
such
as
−CF3,
−OR,
−F,
−Bpin,
−SiR3
groups.
The
synthesized
products
demonstrated
applications
in
coupling
reactions
newly
developed
aza-Giese-type
addition
reaction
(C–N
bond
formation)
from
cyclic
germane
product.
These
versatile
motifs
can
have
a
substantial
value
organic
medicinal
chemistry
they
show
orthogonal
while
competing
other
partners
boranes
or
silanes,
acquiring
three-dimensional
structure
high
stability
robustness.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(29), С. 15695 - 15701
Опубликована: Июль 12, 2023
The
highly
enantioselective
and
complete
hydrogenation
of
protected
indoles
benzofurans
has
been
developed,
affording
facile
access
to
a
range
chiral
three-dimensional
octahydroindoles
octahydrobenzofurans,
which
are
prevalent
in
many
bioactive
molecules
organocatalysts.
Remarkably,
we
control
the
nature
ruthenium
N-heterocyclic
carbene
complex
employed
as
both
homogeneous
heterogeneous
catalysts,
providing
new
avenues
for
its
potential
applications
asymmetric
more
challenging
aromatic
compounds.
Abstract
Asymmetric
sequential
hydrogenations
of
α
‐methylene
γ
‐
or
δ
‐keto
carboxylic
acids
are
established
in
one‐pot
using
a
bimetallic
Ru/Ru
catalyst
system,
achieving
the
stereodivergent
synthesis
all
four
stereoisomers
both
chiral
and
‐lactones
with
two
non‐vicinal
carbon
stereocenters
high
yields
(up
to
99%)
excellent
stereoselectivities
>99%
ee
>20:1
dr).
The
compatibility
Ru
systems
is
investigated
detail,
it
found
that
basicity
reaction
system
plays
key
role
hydrogenation
processes.
protocol
can
be
performed
on
gram‐scale
low
loading
11000
S/C)
resulting
products
allow
for
many
transformations,
particularly
several
intermediates
useful
preparation
drugs
natural
products.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(43), С. 20078 - 20089
Опубликована: Окт. 18, 2022
Rh-catalyzed
sequential
asymmetric
hydrogenations
of
3-amino-4-chromones
have
been
achieved
for
the
first
time
via
an
unprecedented
dynamic
kinetic
resolution
under
neutral
conditions,
providing
(S,R)-3-amino-4-chromanols
in
high
yields
(up
to
98%)
with
excellent
enantio-
and
diastereoselectivities
99.9%
ee
20:1
dr).
The
mechanistic
studies
based
on
control
experiments
density
functional
theory
(DFT)
calculations
suggest
that
process
intermediate
enantiomers
generated
hydrogenation
step
proceeded
a
stereomutation
(or
called
chiral
assimilation)
pathway
from
undesired
enantiomer
desired
rather
than
traditional
racemization
enantiomer.
protocol
can
be
performed
gram
scale
relatively
low
catalyst
loading
offers
practical
convenient
synthesizing
series
bioactive
chromanols
their
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 8, 2023
Herein,
we
show
that
the
combination
of
Birch
reduction
readily
available
anisole
derivatives
and
catalytic
asymmetric
inverse-electron-demand
Diels-Alder
reaction
2-pyrones
can
serve
as
a
powerful
platform
for
diverse
synthesis
synthetically
important
cis-decalin
scaffolds.
Enabled
by
well-modified
chiral
bis(oxazoline)
ligand/CuII
complex,
wide
range
polysubstituted
scaffolds
with
up
to
six
contiguous
stereocenters
were
generated
efficiently.
The
synthetic
potential
this
method
is
demonstrated
concise
sesquiterpene
(+)-occidentalol
key
intermediate
seven
triterpenes.
Mechanistic
studies
suggest
1,3-cyclohexadienes
formed
in
situ
are
intermediates,
efficient
kinetic
resolution
occurs
when
C2-
and/or
C3-substituted
1,4-cyclohexadienes
utilized
substrates.
DFT
calculations
elucidated
proceeds
stepwise
fashion
revealed
origins
stereoselectivities.
