Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(28)
Опубликована: Март 12, 2024
Recently,
chiral
metal-organic
coordination
materials
have
emerged
as
promising
candidates
for
a
wide
range
of
applications
in
chiroptoelectronics,
catalysis,
and
information
encryption,
etc.
Notably,
the
chiroptical
effect
chromophores
makes
them
appealing
such
photodetectors,
OLEDs,
3D
displays,
bioimaging.
The
direct
synthesis
using
organic
ligands
or
complexes
with
metal-centered
chirality
is
very
often
tedious
costly.
In
case
ionic
materials,
combination
anions
cationic,
achiral
compounds
through
noncovalent
interactions
may
endow
molecular
desirable
properties.
use
simple
strategy
has
been
proven
effective
inducing
circular
dichroism
and/or
circularly
polarized
luminescence
signals.
This
concept
article
mainly
delves
into
latest
advances
exploring
efficacy
anion
transforming
superb
photo-
electro-chiroptical
particular,
small-molecular
metal
complexes,
clusters,
supramolecular
assemblies,
frameworks
containing
are
discussed.
A
perspective
on
future
opportunities
preparation
also
presented.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(6), С. 1858 - 1895
Опубликована: Янв. 1, 2024
This
review
is
planned
to
provide
a
comprehensive
overview
of
the
progress
made
in
design
and
development
chiral
ligands
for
asymmetric
gold
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 3598 - 3602
Опубликована: Янв. 31, 2024
Enantioselective
protonation
is
a
versatile
approach
to
the
construction
of
tertiary
α-stereocenters,
which
are
common
structural
motifs
in
various
natural
products
and
biologically
relevant
compounds.
Herein
we
report
mild
access
these
chiral
centers
using
cooperative
gold(I)
catalysis.
From
cyclic
ketone
enol
carbonates,
this
asymmetric
catalysis
provides
highly
enantioselective
ketones
featuring
an
α
center,
including
challenging
2-methylsuberone.
In
combination
with
gold-catalyzed
formation
cyclopentadienyl
carbonates
one-pot,
two-step
process,
chemistry
enables
expedient
synthetically
α′-chiral
cyclopentenones
excellent
enantiomeric
excesses
from
easily
accessible
enynyl
carbonate
substrates.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 31, 2025
ConspectusFunctionalization
of
alkynes
is
an
established
cornerstone
organic
synthesis.
While
numerous
transition
metals
exhibit
promising
activities
in
the
transformations
via
π-insertion
or
oxidative
cyclometalation,
Lewis
π-acids
offer
a
different
approach.
By
coordinating
with
through
π-bonding,
facilitate
nucleophilic
addition,
leading
to
formation
alkenyl
metal
species.
These
species
can
undergo
electron
rearrangement
generate
carbenes,
which
are
crucial
intermediates
for
subsequent
carbene
transfer
reactions.
This
reaction
pathway
provides
versatile
route
alkyne
functionalization,
especially
asymmetric
manner.
Although
π-acid,
gold(I),
pioneered
this
mode,
development
variants
remains
challenging
due
linear
coordination
gold(I).
Therefore,
expanding
range
catalysts
beyond
gold(I)
complexes
other
would
further
advances
chiral
molecule
construction
and
exploration
novel
modes.In
Account,
we
present
concise
review
multifunctionalization
dirhodium-catalyzed
transformations,
providing
modulation
strategies
substrates
plausible
mechanisms.
In
aromatization-driven
strategy,
furanyl
dirhodium
generated
from
enynone,
terminated
by
enantioselective
intramolecular
C-H
insertion,
cyclopropanation,
aromatic
substitution,
Büchner
reaction,
giving
dihydroindoles,
dihydrobenzofurans,
cyclopropane-fused
tetrahydroquinolines,
fluorenes,
cyclohepta[b]benzofurans.
The
cap-tether
strategy
was
developed
study
balance
reactivity
selectivity
azo-enyne.
gave
first
catalytic
cycloisomerization
azo-enyne,
affording
centrally
axially
isoindazole
derivatives.
synergistic
activation
i.e.,
EWG
C-H···O
interaction,
introduced
achieve
enynes,
cyclopropane-annulated
bicyclic
systems
enynals.
Benefiting
these
successes,
difluoromethyl-substituted
enynes
were
designed
proven
be
effective
substrates.
With
corresponding
benzo-1,6-enynes
as
substrates,
biscyclopropanation
cascaded
cyclopropanation/cyclopropenation
achieved
using
dicarbene
equivalents.
Additionally,
benzo-1,5-enynal
vinyl
carbene,
reacted
variety
alkenes
[2
+
1]
cycloaddition,
[4
3]
formal
allylation,
spiro
fused
polycyclic
heterocycles.
Coupling
desymmetrization,
successfully
diynals,
constructing
furan-fused
dihydropiperidines
alkyne-substituted
aza-quaternary
stereocenter.
Notably,
analyzing
X-ray
structures
several
dirhodium-alkyne
π-complexes,
together
results
DFT
calculations
control
experiments,
obtained
evidence
supporting
making
well-defined
paddlewheel-like
dirhodium(II)
stand
out
among
complexes.
We
anticipate
that
our
research
will
significantly
advance
fields
dirhodium,
alkyne,
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(40)
Опубликована: Авг. 4, 2022
Abstract
An
asymmetric
para‐
C(sp
2
)−H
bond
functionalization
of
alkyl
benzene
derivatives
was
successfully
developed
via
cooperative
catalysis
gold
and
chiral
phosphoric
acid
(CPA),
leading
to
synthetically
useful
1,1‐diaryl
motifs.
Chiral
acid,
ligand,
molecular
sieves
were
found
be
crucial
for
enantioselectivity
control
this
transformation.
The
salient
features
protocol
include
mild
conditions,
high
efficiency,
commercially
available
starting
materials,
highly
chemo‐
site‐
as
well
enantioselective
aromatic
C−H
functionalization,
broad
substrate
scope,
extensive
applications
the
products.
mechanistic
studies
suggested
that
two
CPAs
might
involved
in
induction.
Organometallics,
Год журнала:
2024,
Номер
43(2), С. 69 - 84
Опубликована: Янв. 8, 2024
Activation
of
halido
gold(I)
precatalysts
Au(L)X
to
a
cationic
species
[Au(L)]+
with
vacant
coordination
site
for
substrate
binding
typically
requires
abstraction
the
halide
X–.
The
Fischer-type
carbene
2–4
feature
redox-active
dimethylanilinyl,
2-furyl,
and
ferrocenyl
substituents
without
(2a–4a)
(2b–4b),
dangling
dimethylamino
substituent.
After
single-electron
oxidation,
catalyze
cyclization
N(2-propyn-1-yl)benzamide
2-phenyl-5-vinylidene-2-oxazoline
presence
scavenger.
While
all
dimethylanilinyl
2-furyl
substituted
likely
form
catalytically
active
nanoparticles
after
complexes
4a
4b
operate
in
homogeneous
fashion.
precatalyst
is
most
one.
formation
molecular
oxidation
was
probed
by
stopped-flow
experiments,
quantitative
EPR
spectroscopy,
quantum
chemical
calculations
arrive
at
consistent
mechanistic
picture
that
involves
one-electron
ferrocene,
valence
isomerization
gold(II)
anion
center.
This
oxidation/isomerization/coordination
activation
mechanism
fundamentally
different
from
typical
opens
new
avenues
gold
catalysis
beyond
gold(III)
catalyses.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2308 - 2312
Опубликована: Янв. 18, 2024
Bifunctional
ligand-enabled
cooperative
gold
catalysis
accelerates
nucleophilic
attacks
and
offers
a
versatile
strategy
to
achieve
asymmetric
catalysis.
Distinct
from
the
prior
studies
employing
alkyne/allene
as
electrophilic
site,
this
work
engages
an
in
situ-generated
alkenyl/acyl
carbene
ligand-facilitated
attack
by
alcoholic
nucleophile.
With
amide-functionalized
chiral
binaphthylphosphine
ligand,
γ-alkoxy-α,β-unsaturated
imides
are
formed
with
excellent
enantiomeric
excesses.
The
intermediacy
of
species
is
supported
its
alternative
access
via
dediazotization.
reaction
tolerates
broad
range
alcohols
can
accommodate
dienynamide
substrates,
addition
arylenynamides.
This
avails
enrich
chemistry
challenging
enantioselective
trapping
reactive
intermediates.
JACS Au,
Год журнала:
2023,
Номер
3(6), С. 1742 - 1754
Опубликована: Май 26, 2023
A
new
generation
of
chiral
gold(I)
catalysts
based
on
variations
complexes
with
JohnPhos-type
ligands
a
remote
C2-symmetric
2,5-diarylpyrrolidine
have
been
synthesized
different
substitutions
at
the
top
and
bottom
aryl
rings:
from
replacing
phosphine
by
N-heterocyclic
carbene
(NHC)
to
increasing
steric
hindrance
bis-
or
tris-biphenylphosphine
scaffolds,
directly
attaching
C2-chiral
pyrrolidine
in
ortho-position
dialkylphenyl
phosphine.
The
tested
intramolecular
[4+2]
cycloaddition
arylalkynes
alkenes
atroposelective
synthesis
2-arylindoles.
Interestingly,
simpler
led
formation
opposite
enantiomers.
binding
pockets
analyzed
DFT
calculations.
As
revealed
non-covalent
interaction
plots,
attractive
interactions
between
substrates
direct
specific
enantioselective
folding.
Furthermore,
we
introduced
open-source
tool
NEST,
specifically
designed
account
for
effects
cylindrical-shaped
complexes,
which
allows
predicting
experimental
enantioselectivities
our
systems.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
146(1), С. 733 - 741
Опубликована: Дек. 27, 2023
Transition-metal-catalyzed
enantioselective
N–H
insertion
reactions
of
carbene
species
offer
a
powerful
and
straightforward
strategy
to
produce
chiral
nitrogen-containing
compounds.
Developing
highly
selective
using
indole
variants
can
meet
synthetic
demand.
Herein
we
present
an
asymmetric
reaction
into
bonds
the
aromatic
heterocycles
donor/acceptor-substituted
diazo
compounds
based
on
heteronuclear
catalytic
platform.
Although
previously
developed
catalysis
comprising
silver
catalyst
or
dirhodium(II,II)
paddlewheel
complexes
with
without
phosphoric
acid
showed
modest
performance,
unique
combination
widely
available
Rh2(OAc)4
silver(I)
phosphate
dimer
[(S)-TRIP-Ag]2
enabled
(up
98%
ee).
Moreover,
Ag/Rh
system
facilitated
regioselective
C–H
functionalization
protic
indoles.
Mechanistic
investigation
density
functional
theory
indicated
that
in
situ-generated
Ag–Rh
trimetallic
enolate
is
protonated
environment.