Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(26), P. 10396 - 10400
Published: March 25, 2020
This
work
reports
gold-catalyzed
[4+3]-annulations
of
2-(1-alkynyl)-2-alken-1-ones
with
anthranils
to
yield
epoxybenzoazepine
products
excellent
exo-diastereoselectivity
(dr>25:1).
The
utility
this
new
gold
catalysis
is
manifested
by
applicable
substrates
over
a
broad
scope.
More
importantly,
the
enantioselective
versions
these
[4+3]-cycloadditions
have
been
developed
satisfactorily
chiral
catalysts
under
ambient
conditions
(DCM,
0
°C);
ee
levels
range
from
88.0-99.9
%.
With
DFT
calculations,
we
postulate
stepwise
pathway
rationalize
preferable
exo-stereoselection.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(14), P. 8685 - 8755
Published: Nov. 12, 2020
The
past
decade
has
witnessed
the
golden
age
of
homogeneous
gold-catalyzed
reactions,
especially
those
that
involve
transformation
highly
strained
molecules
into
complex
molecular
architectures.
Gold
catalysts,
with
unique
electronic
properties
and
catalytic
abilities,
have
elevated
versatile
reaction
modes
through
π-interaction
induced
activation.
On
basis
increasing
research
interest
in
this
topic,
together
significant
development
various
ligands,
including
phosphine
ligands
azacyclic
or
noncyclic
carbene
understanding
function
gold
catalysts
become
much
deeper
more
comprehensive.
Different
needs
thus
could
be
adapted
by
a
novel
catalyst
diversified
ligand
selection.
Furthermore,
whole
evolution
catalysis
on
synthetic
methodologies
realized
expanded
its
application
natural
product
synthesis
as
well
potentiality
drug
discovery,
which
endows
ancient
metal
magnificent
renaissance.
reactivity
small
ring
high
tension
always
been
an
important
topic
organic
chemistry.
When
is
linked
π-electron
rich
moiety
contains
heteroatom,
activation
π-system
coordination
heteroatom
can
initiate
cascade
reaction,
usually
followed
opening
expansion.
These
processes
result
rapid
construction
distinct
structures,
many
feature
biologically
molecules.
In
review,
we
will
mainly
summarize
advances
diverse
types
constructions
accomplished
using
substrates,
methylenecyclopropanes
(MCPs),
vinylidenecyclopropanes
(VDCPs),
cyclopropenes
aziridine-
epoxide-containing
molecules,
focusing
last
10
years.
For
functionalized
alkynyl
cyclopropanes,
several
early
inspiring
elegant
examples
described
review
for
systematically
these
transformations.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(32), P. 11016 - 11019
Published: Aug. 3, 2017
The
development
of
a
gold(III)
catalyzed
direct
enantioconvergent
1,5-enyne
cycloisomerization
and
kinetic
resolution
reaction
is
described.
transformation
results
in
highly
enantioenriched
bicyclo[3.1.0]hexenes
at
all
levels
conversion,
with
no
racemization
or
symmetrization
taking
place
during
the
course
reaction,
simultaneously
affords
optically
enriched
1,5-enynes.
This
report
marks
first
enantioselective
by
well-defined
cationic
catalyst
demonstrates
unique
potential
complexes
catalysis.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(8), P. 3797 - 3805
Published: Feb. 3, 2020
Tethering
a
metal
complex
to
its
phosphate
counterion
via
phosphine
ligand
enables
new
strategy
in
asymmetric
counteranion-directed
catalysis
(ACDC).
A
straightforward,
scalable
synthetic
route
gives
access
the
gold(I)
of
displaying
chiral
phosphoric
acid
function.
The
generates
catalytically
active
species
with
an
unprecedented
intramolecular
relationship
between
cationic
Au(I)
center
and
counterion.
benefits
tethering
two
functions
catalyst
are
demonstrated
here
tandem
cycloisomerization/nucleophilic
addition
reaction,
by
attaining
high
enantioselectivity
levels
(up
97%
ee)
at
unusually
low
0.2
mol
%
loading.
Remarkably,
method
is
also
compatible
silver-free
protocol.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(37), P. 12943 - 12946
Published: Sept. 8, 2017
Computed
descriptors
for
acyclic
diaminocarbene
ligands
are
developed
in
the
context
of
a
gold
catalyzed
enantioselective
tandem
[3,3]-sigmatropic
rearrangement-[2+2]-cyclization.
Surrogate
structures
enable
rapid
identification
parameters
that
reveal
mechanistic
characteristics.
The
observed
selectivity
trends
validated
robust
multivariate
analysis
facilitating
development
highly
process.
Chemistry - An Asian Journal,
Journal Year:
2021,
Volume and Issue:
16(5), P. 364 - 377
Published: Jan. 2, 2021
Asymmetric
gold
catalysis
has
been
rapidly
developed
in
the
past
ten
years.
Breakthroughs
have
made
by
rational
design
and
meticulous
selection
of
chiral
ligands.
This
review
summarizes
newly
gold-catalyzed
enantioselective
organic
transformations
recent
progress
ligand
(since
2016),
organized
according
to
different
types
ligands,
including
bisphosphine
monophosphine
phosphite-derived
N-heterocyclic
carbene
ligands
for
asymmetric
gold(I)
as
well
heterocyclic
oxazoline
gold(III)
catalysis.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(8), P. 3497 - 3509
Published: Feb. 9, 2022
A
new
strategy
for
enantioselective
transition-metal
catalysis
is
presented,
wherein
a
H-bond
donor
placed
on
the
ligand
of
cationic
complex
allows
precise
positioning
chiral
counteranion
responsible
asymmetric
induction.
The
successful
implementation
this
paradigm
demonstrated
in
5-exo-dig
and
6-endo-dig
cyclizations
1,6-enynes,
combining
an
achiral
phosphinourea
Au(I)
chloride
with
BINOL-derived
phosphoramidate
Ag(I)
salt
thus
allowing
first
general
use
anions
Au(I)-catalyzed
reactions
challenging
alkyne
substrates.
Experiments
modified
complexes
anions,
1H
NMR
titrations,
kinetic
data,
studies
solvent
nonlinear
effects
substantiate
key
H-bonding
interaction
at
heart
catalytic
system.
This
conceptually
novel
approach,
which
lies
intersection
metal
catalysis,
organocatalysis,
counterion-directed
provides
blueprint
development
supramolecularly
assembled
ligands
complexes.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(20)
Published: Jan. 11, 2022
Abstract
Transition
metal‐catalyzed
enantioselective
functionalization
of
ubiquitous
C−H
bonds
has
proven
to
be
promising
field
as
it
offers
the
construction
chiral
molecular
complexity
in
a
step‐
and
atom‐economical
manner.
In
recent
years,
gold
emerged
an
attractive
contender
for
catalyzing
such
reactions.
The
unique
reactivities
selectivities
offered
by
catalysts
have
been
exploited
access
numerous
asymmetric
transformations
based
on
gold‐catalyzed
processes.
Herein,
this
review
critically
highlights
major
advances
discoveries
made
under
catalysis
which
is
accompanied
mechanistic
insights
at
appropriate
places.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(6), P. 1858 - 1895
Published: Jan. 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.
