Organic & Biomolecular Chemistry,
Год журнала:
2018,
Номер
17(6), С. 1395 - 1401
Опубликована: Дек. 20, 2018
A
newly
developed
Ming-Phos
ligand
with
a
3,5-bis(trifluoromethyl)phenyl
substituent
was
demonstrated
to
be
highly
efficient
for
Ag-catalyzed
asymmetric
[3
+
2]
cycloaddition
reactions
of
azomethine
ylides
maleimides,
cyclopentene-1,3-diones,
and
N-(2-t-butylphenyl)maleimide.
Being
easily
prepared
on
the
gram
scale
in
one
step,
combination
Ag
catalyst
enables
synthesis
variety
functionalized
bicyclic
pyrrolidine
derivatives
good
yields
excellent
enantioselectivities
under
mild
conditions.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(8), С. 3797 - 3805
Опубликована: Фев. 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.
Accounts of Chemical Research,
Год журнала:
2020,
Номер
53(10), С. 2358 - 2371
Опубликована: Окт. 1, 2020
ConspectusA
small-molecule
collection
with
structural
diversity
and
complexity
is
a
prerequisite
to
using
either
drug
candidates
or
chemical
probes
for
discovery
chemical–biology
investigations,
respectively.
Over
the
past
12
years,
we
have
engaged
in
developing
efficient
diversity-oriented
cascade
strategies
synthesis
of
topologically
diverse
skeletons
incorporating
biologically
relevant
motifs
such
as
O-
N-heterocycles,
fused
polycycles,
multifunctionalized
allenes.
In
particular,
highlighted
use
simple,
linear,
densely
functionalized
molecular
platforms
these
reactions.This
account
details
our
efforts
design
novel
metal-
organo-catalyzed
reactions,
which
include
2-(1-alknyl)-2-alken-1-ones
(yne–enones)
heterocyclization/cross-coupling
cascades,
heterocyclization/cycloaddition
nucleophilic
addition/cross-coupling
addition/heterocyclization
so
on.
Moreover,
this
Account
outlines
corresponding
mechanistic
insights,
computational
information,
applications
cascades
construction
various
highly
substituted
carbo-
heterocycles
well
acyclic
compounds,
e.g.,
allenes
dienes.
addition
yne–enones,
evolved
functional
groups
original
yne–enones
provide
series
yne–enone
variants,
resulted
products
complementary
reactivities.The
reactivity
profile
defined
by
presence
an
alkyne
moiety
conjugated
enone
unit
their
mutual
through-bond
connectivity.
Owing
conceptually
rapid
development
carbophilic
activation,
identified
catalytic
systems
consisting
metal
catalysts,
including
Pd,
Au,
Rh
complexes,
catalysis,
allowing
unprecedented
reactions
be
achieved
through
different-types
reaction
intermediates,
all-carbon
1,n-dipoles,
furan-based
o-quinodimethanes
(oQDMs),
allenyl-metal
species.
commonly
known
transition-metal
activity,
Lewis
acidity
complexes
crucial
accomplish
transformation.
addition,
enantioselective
gold(I)-catalyzed
variants
were
application
bisphosphines
(e.g.,
Cn-TunePhos),
monophosphines,
developed
"Ming–Phos"
chiral
ligands.
Importantly,
Ming–Phos
ligands
exhibited
excellent
performance
gold-catalyzed
mechanistically
distinct
[3
+
n]-cycloaddition
sulfinamide
possibly
responsible
interaction
substrate
control
enantioselectivity.
Subsequently,
demonstrated
that
easily
prepared
polymer-supported
ligand
could
applied
heterogeneously
asymmetric
cycloaddition
good
stereocontrol.
With
metal-free
divergent
functionalization
provides
numerous
synthetic
outlets
structure
diversification.
For
example,
are
particularly
attractive
precursors
achiral
heterocycles,
pyrazoles,
isoxazoles,
pyrroles,
pyrans,
etc.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(33), С. 11444 - 11448
Опубликована: Июнь 14, 2019
Abstract
Reported
herein
is
an
asymmetric
Pd/PC‐Phos‐catalyzed
denitrogenative
cyclization
of
benzotriazoles
with
allenes
and
N‐allenamides,
representing
the
first
example
enantioselective
cyclizations
benzotriazoles.
A
series
optically
active
3‐methyleneindolines
were
obtained
in
good
yields
high
ee
values.
The
use
inexpensive
readily
available
starting
materials,
regio‐
enantioselectivity,
a
broad
substrate
scope,
mild
reaction
conditions,
no
need
for
base,
as
well
versatile
functionalization
make
this
approach
attractive.
Chemistry - An Asian Journal,
Год журнала:
2021,
Номер
16(5), С. 364 - 377
Опубликована: Янв. 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.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(49), С. 21991 - 21996
Опубликована: Сен. 2, 2020
Abstract
A
palladium‐catalyzed
intermolecular
dynamic
kinetic
asymmetric
dearomatization
of
3‐arylindoles
with
internal
alkynes
was
developed
the
use
achiral
Xantphos
and
chiral
sulfinamide
phosphine
ligand
(
PC‐Phos
)
as
co‐ligands.
This
method
could
deliver
various
spiro[indene‐1,3′‐indole]
compounds
in
good
yields
(up
to
95
%
yield)
up
98
ee
.
The
salient
features
transformation
include
readily
available
substrates,
ease
scale‐up
versatile
functionalization
products.
mechanistic
experiments
gave
some
insights
on
active
intermediates.
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:
2019,
Номер
141(30), С. 11858 - 11863
Опубликована: Июль 10, 2019
Chiral
gold(I)
catalysts
have
been
designed
based
on
a
modified
JohnPhos
ligand
with
distal
C2-2,5-diarylpyrrolidine
that
creates
tight
binding
cavity.
The
C2-chiral
element
is
close
to
where
the
C–C
bond
formation
takes
place
in
cyclizations
of
1,6-enynes.
These
chiral
mononuclear
applied
for
enantioselective
5-exo-dig
and
6-endo-dig
cyclization
different
1,6-enynes
as
well
first
total
synthesis
three
members
carexane
family
natural
products.
Opposite
enantioselectivities
achieved
seemingly
analogous
reactions
1,6-enynes,
which
result
from
folding
substrates
attractive
aryl–aryl
interactions.
Organic Letters,
Год журнала:
2019,
Номер
21(9), С. 3018 - 3022
Опубликована: Апрель 17, 2019
The
highly
exo-
and
enantioselective
gold-catalyzed
tandem
heterocyclization/[4
+
3]
cycloaddition
of
2-(1-alkynyl)-2-alken-1-ones
1,3-diphenylisobenzofuran
was
implemented
by
utilizing
Ming-Phos,
which
provides
a
facile
access
to
chiral
seven-membered
oxa-bridged
rings
in
80-98%
yield
with
high
exo
selectivity
(
exo/
endo
up
50:1)
97%
ee.
ChemPlusChem,
Год журнала:
2021,
Номер
86(9), С. 1283 - 1296
Опубликована: Июль 12, 2021
Abstract
Gold(I)
catalysts
are
ideal
for
the
activation
of
alkynes
under
very
mild
conditions.
However,
unlike
allenes
or
alkenes,
triple
bond
cannot
be
prochiral.
In
addition,
linear
coordination
displayed
by
gold(I)
complexes
places
chiral
ligand
far
away
from
substrate
resulting
in
an
inefficient
transfer
information.
This
poses
a
significant
challenge
achievement
high
enantiocontrol
gold(I)‐catalyzed
reactions
alkynes.
Although
considerable
progress
on
enantioselective
transformations
has
recently
been
achieved,
asymmetric
non‐prochiral
alkyne‐containing
small
molecules
still
represents
great
challenge.
Herein
we
summarize
recent
advances
intra‐
and
intermolecular
involving
alkynes,
discussing
new
designs
that
lie
at
basis
these
developments.
We
also
focus
mode
action
catalysts,
their
possible
limitations
towards
next‐generation
more
efficient
designs.
Finally,
square
planar
gold(III)
complexes,
which
offer
alternative
to
discussed.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(17), С. 9339 - 9344
Опубликована: Фев. 12, 2021
Chiral
gold(I)-cavitand
complexes
have
been
developed
for
the
enantioselective
alkoxycyclization
of
1,6-enynes.
This
cyclization
has
applied
first
total
synthesis
carbazole
alkaloid
(+)-mafaicheenamine
C
and
its
enantiomer,
establishing
configuration
as
R.
The
cavity
effect
was
also
evaluated
in
cycloisomerization
dienynes.
A
combination
experiments
theoretical
studies
demonstrates
that
gold(I)
forces
enynes
to
adopt
constrained
conformations,
which
results
high
observed
regio-
stereoselectivities.
