European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
Abstract
Ligands
play
a
key
role
in
asymmetric
transition‐metal
catalysis.
Among
reported
chiral
ligands,
readily
available
and
air‐stable
secondary
phosphine
oxide
ligands
are
unique
have
aroused
wide
interest
Ni−Al
bimetallic
catalysis,
since
they
can
act
as
bifunctional
to
ligate
two
metals
for
stronger
synergism,
greatly
enhancing
reactivity
selectivity.
Hence,
this
mini
review
we
will
focus
on
oxides
their
applications
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1147 - 1157
Опубликована: Янв. 3, 2025
This
study
describes
a
photoredox/cobalt
dual-catalyzed
asymmetric
Grignard-type
addition
reaction,
enabling
the
synthesis
of
axially
chiral
hexatomic
(six–six)
N-heterobiaryls
bearing
extra
secondary
alcohol
unit
via
an
efficient
dynamic
kinetic
transformation
racemic
N-heterobiaryl
triflate
substrates.
The
conversion
facilitated
both
photoredox
and
classical
reductive
reaction
conditions
exhibits
good
functional
group
tolerance,
broad
substrate
scope,
satisfactory
stereoselectivity.
Furthermore,
control
experiments
density
theory
calculations
provide
preliminary
mechanistic
insights.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11165 - 11206
Опубликована: Янв. 1, 2024
This
review
explores
the
fascinating
world
of
molecules
featuring
multiple
stereogenic
elements,
unraveling
different
strategies
designed
over
years
for
their
enantioselective
synthesis.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
A
novel
mechanism
for
N-heteroaryl
C–H
functionalization
via
dearomative
addition-hydrogen
autotransfer
is
described.
Upon
exposure
to
the
catalyst
derived
from
RuHCl(CO)(PPh3)3
and
Xantphos,
dienes
1a–1g
suffer
hydroruthenation
form
allylruthenium
nucleophiles
that
engage
in
addition-β-hydride
elimination
furnish
branched
products
of
C–C
coupling
3a–3s
4a–4f.
Oxidative
cleavage
isoprene
adducts
3j,
3k,
3l,
3n
followed
by
ruthenium-catalyzed
dynamic
kinetic
asymmetric
ketone
reduction
provides
enantiomerically
enriched
N-heteroarylethyl
alcohols
6a–6d
and,
therefrom,
amines
7a–7d.
Density
functional
theory
calculations
correlate
experimentally
observed
regioselectivities
with
magnitude
LUMO
coefficients
corroborate
rate-determining
addition.
In
presence
2-propanol
trifluoroethanol,
dearomatized
pyrimidine
2a
quinazoline
2n
were
isolated
characterized.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Organocatalytic
atropisomeric
synthesis
with
fluorinated
oxindoles
and
4-halo-3-nitrocoumarins
gives
congested
structures
displaying
a
Csp2-Csp3
chirality
axis
an
adjacent
tetrasubstituted
stereogenic
carbon
center
good
yields,
up
to
97%
ee
41
:
1
dr.
The
scalable
dehalogenative
C-C
bond
formation
is
achieved
under
mild
conditions
commercially
available
urea
catalyst.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(23), С. 6819 - 6849
Опубликована: Янв. 1, 2024
This
review
highlights
recent
advances
in
the
atroposelective
preparation
of
axially
chiral
azole
derivatives,
emphasizing
mechanistic
insights
and
synthetic
applications
development
this
class
five-membered
heterocyclic
frameworks.
JACS Au,
Год журнала:
2024,
Номер
4(11), С. 4445 - 4454
Опубликована: Окт. 14, 2024
The
development
of
chiroptical
molecular
switches
for
chiral
sensing,
data
communication,
optical
displays,
logic
gates,
and
asymmetric
catalysis
is
currently
a
vibrant
frontier
science
technology.
Herein,
we
report
practical
artificial
dynamic
system
based
on
1,2-diaxial
atropisomer.
Organocatalytic
parallel
kinetic
resolution
allows
the
divergent
synthesis
two
sets
stereoisomers
with
vicinal
C-C
N-N
axes
from
same
racemic
single-axis
substrates.
By
simply
varying
configuration
single
catalyst,
all
four
are
accessible.
successive
conduction
covalent
unlocking/locking
thermal-isomerization
processes
enables
sequential
switching
between
atropisomeric
states
electronic
circular
dichroism
signal
reversal,
providing
an
example
multistate
switches.
A
novel
P(═O)R2-directed
asymmetric
catalytic
olefination
has
been
developed,
enabling
efficient
access
to
carbon–nitrogen
axially
chiral
products
with
excellent
yields
(up
92%)
and
enantioselectivity
99%
enantiomeric
excess).
The
synergistic
coordination
of
phosphine
oxide
functionality
l-pGlu-OH
the
Pd
metal
center,
serving
as
an
directing
group
ligand,
was
key
success
this
C–H
functionalization
system.
reaction
demonstrated
a
broad
substrate
scope,
yielding
33
distinct
C–N
axial
products.
absolute
configuration
unambiguously
confirmed
via
X-ray
diffraction
analysis.
Additionally,
three
representative
applications
were
showcased,
involving
reduction
oxidation
produce
phosphines
related
derivatives.
plausible
cycle
mechanism
proposed,
supported
by
detailed
experimental
studies.
Aggregates
in
system
identified
aggregation-induced
polarization
experiments.
Chemical Communications,
Год журнала:
2024,
Номер
60(62), С. 8008 - 8019
Опубликована: Янв. 1, 2024
Reductive
elimination
is
a
key
step
in
Ni-catalysed
cross-couplings,
which
often
considered
to
result
new
covalent
bonds.
Due
the
weak
oxidizing
ability
of
Ni(II)
species,
reductive
eliminations
from
centers
are
challenging.
A
thorough
mechanistic
understanding
this
process
could
inspire
rational
design
coupling
reactions.
In
article,
we
give
an
overview
recent
advances
study
species
achieved
by
our
group.
Three
possible
models
for
were
investigated
and
discussed,
including
direct
elimination,
electron
density-controlled
oxidation-induced
elimination.
Notably,
requires
high
activation
energy
some
cases.
contrast,
pathways
can
significantly
enhance
driving
force
accelerating
formation
The
intricate
reaction
mechanisms
each
these
thoroughly
discussed
systematically
summarized
paper.
These
computational
studies
showcase
characteristics
three
hope
that
it
will
spur
development
cross-coupling