Herein,
we
report
a
gold(I)-catalyzed
heterocyclization/(5
+
3)
cycloaddition
cascade
of
yne-enones
with
imidazolidines,
providing
modular,
atom-economical
and
efficient
strategy
for
the
synthesis
cycloocta[c]furans
in
moderate
to
excellent
yields.
This
method
features
readily
available
substrates,
simple
operation,
mild
reaction
conditions,
broad
substrate
scope.
More
importantly,
asymmetric
version
is
also
achieved
by
employing
(R)-C2-TunePhos
ligand
(L7),
leading
optically
active
up
98:2
er.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(10), С. 4146 - 4174
Опубликована: Янв. 1, 2022
The
advances
on
metal-catalysed
high-order
dipolar
annulations
were
comprehensively
summarized
in
this
review.
To
further
exploit
the
potential
of
unique
annulation
strategy,
a
research
outlook
was
also
proposed.
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.
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(8), С. 4378 - 4383
Опубликована: Фев. 16, 2023
2,3-Dihydrobenzofurans
are
crucial
building
blocks
in
the
synthesis
of
natural
products
and
pharmaceutical
molecules.
However,
their
asymmetric
has
been
a
long-standing
formidable
challenge
so
far.
In
this
work,
we
developed
highly
enantioselective
Pd/TY-Phos-catalyzed
Heck/Tsuji-Trost
reaction
o-bromophenols
with
various
1,3-dienes,
allowing
expedient
access
to
chiral
substituted
2,3-dihydrobenzofurans.
This
features
excellent
regio-
enantiocontrol,
high
functional
group
tolerance,
easy
scalability.
More
importantly,
demonstration
method
as
valuable
tool
for
construction
optically
pure
(R)-tremetone
fomannoxin
is
highlighted.
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.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(26), С. 10396 - 10400
Опубликована: Март 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.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1741 - 1749
Опубликована: Янв. 18, 2024
An
asymmetric
cascade
cyclization
of
enynamides
and
α-diazoketones
to
produce
chiral
bicyclic
lactams
bearing
all-carbon
quaternary
stereocenters
is
realized
with
up
95%
yield,
98%
ee,
>19:1
dr.
The
combination
visible
light
photoactivation
the
relay
gold
N-oxide
catalysis
in
a
process
enabled
facile
generation
controlled
assembly
two
reactive
intermediates,
ketene
aza-o-quinone
methide.
Theoretical
calculations
revealed
stepwise
[4
+
2]
cycloaddition
mechanism,
stereochemistry
by
amide
group
catalyst.
Remarkably,
this
study
presents
first
example
N-oxides
serving
as
catalysts
for
illustrates
how
strategy
could
be
promising
means
access
significant
heterocyclic
scaffolds.
Organic Letters,
Год журнала:
2019,
Номер
21(16), С. 6245 - 6248
Опубликована: Авг. 1, 2019
A
new
[3
+
4]
cycloaddition
of
azaoxyallyl
cations
and
anthranils
has
been
achieved
for
rapid
access
to
multisubstituted
benzodiazepine
derivatives.
variety
α-halo
hydroxamates
were
both
effective
substrates
with
simple
operations
under
transition-metal-free
conditions.
The
intriguing
features
this
method
include
its
mild
nature
the
reaction
conditions,
high
efficiency,
broad
substrate
scope,
wide
functional
group
compatibility.
