The Chemical Record,
Journal Year:
2022,
Volume and Issue:
23(3)
Published: Dec. 21, 2022
Abstract
This
review
summarizes
recent
developments
(from
2006
to
2022)
in
numerous
important
and
efficient
carbo‐
heterocycle
generations
using
gold‐catalyzed
cascade
protocols.
Herein,
methodologies
involve
selectivity,
cost‐effectiveness,
ease
of
product
formation
being
controlled
by
the
ligand
as
well
counter
anion,
catalyst,
substrate,
reaction
conditions.
Gold‐catalyzed
reactions
covered
different
strategies
through
compilation
various
approaches
such
cyclization,
hydroarylation,
intermolecular
intramolecular
reactions,
etc.
entitled
is
also
useful
for
synthesis
spiro,
fused,
bridged
heterocycles.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: April 8, 2023
Abstract
The
use
of
ynamides
in
organic
synthesis
has
gained
significant
attention
due
to
their
ability
provide
access
complex
molecular
structures
through
transformations
such
as
1,2‐difunctionalization
and
annulation
reactions.
These
reactions
enable
the
formation
highly
functionalized
N‐bearing
olefins
unusual
heterocycles.
In
this
minireview,
we
present
a
systematic
overview
regioselective
difunctionalization
ynamides.
We
discuss
multi‐component
reactions,
radical‐triggered
functionalizations
across
carbon–carbon
multiple
bonds
bifunctional
reagents
ynamides,
highlighting
potential
expanding
substrate
scope.
Furthermore,
insights
into
mechanistic
breakthroughs
that
have
been
achieved
recent
years
development
these
Finally,
emphasize
promising
future
prospects
versatile
building
blocks
for
architectures.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(12), P. 1406 - 1420
Published: June 6, 2023
ConspectusLate-transition-metal-based
complexes
represent
an
indispensable
catalytic
tool
in
chemical
synthesis
due
to
their
ability
increase
molecular
complexity
rapidly
and
efficiently
from
readily
accessible
substrates
a
single
operation.
Added
this
is
the
exquisite
control
of
product
chemo-,
diastereo-,
enantio-,
site-selectivities
achieved
by
systems
transition-metal
salts
that
have
been
developed
mediate
wide
range
functional
group
transformations.
Within
venerable
synthetic
toolbox,
Au(I)
Au(III)
emerged
recent
years
as
invaluable
addition
result
potent
σ-
π-Lewis
acidities
stabilize
cationic
reaction
intermediates.
The
insights
provided
mechanistic
studies
examining
various
electronic,
steric,
stereoelectronic
factors
at
play
organogold
species
are
expected
be
formed
chemistry
complex
also
pivotal
understanding
exploring
potential
utility.
Illustrative
this,
for
example,
contribution
made
gold-catalyzed
cycloisomerization
propargyl
esters
strategies
variety
bioactive
natural
products
compounds
current
pharmaceutical
materials
interest.
This
Account
summarizes
our
efforts
over
past
decade
toward
realizing
new
single-step
carbocyclic
heterocyclic
relied
on
reactions
esters.
It
outlines
methods
exploited
unique
reactivities
gold-carbene
typically
generated
[2,3]-sigmatropic
rearrangement
compound
class
containing
terminal
or
electron-deficient
alkyne
moiety
exposure
salt.
describes
realization
initiated
1,3-acyloxy
migration
with
electronically
unbiased
disubstituted
C≡C
bond
delivers
corresponding
allenyl
ester
primed
further
reactivity
activation
11
metal
complex.
part
ongoing
overarching
program
within
was
focused
determining
gold
catalysis
would
enable
application
recognizable
disconnections
retrosynthetic
analysis.
They
were
additionally
aimed
evaluating
opportunities
offered
relativistic
effects
possessed
complex,
most
pronounced
among
d-block
elements
thus
catalyst
choice
chemistry,
generate
space.
For
instance,
we
demonstrated
several
1,3-
1,4-enyne
reliable
strategy
situ
formation
1,4-cyclopentadienyl
derivatives.
Their
appropriately
placed
second
starting
material
then
shown
afford
targets
five-membered
ring
structure.
An
example
assembly
member
1H-isoindole
family
found
exhibit
TNF-α
(tumor
necrosis
factor-α)
inhibitor
activity.
Herein,
we
report
an
HFIP-mediated,
versatile,
sustainable,
atom-economical,
and
regio-
stereoselective
hydro-functionalization
of
ynamides
with
various
S-nucleophiles
(1
equiv.)
such
as
thiols,
thiocarboxylic
acids,
carbamates,
xanthates,
O,O-diethyl
S-hydrogen
phosphorothioate
to
access
a
wide
variety
stereodefined
trisubstituted
ketene
N,S-acetals
under
mild
conditions.
This
protocol
requires
only
HFIP,
which
plays
multiple
roles,
acting
Brønsted
acid
protonate
the
ynamide
regioselectively
at
beta
carbon
generate
reactive
keteniminium
intermediate,
stabilizing
intermediate
solvent
through
H-bonding.
After
nucleophilic
attack
S-nucleophile
on
deprotonation,
HFIP
is
regenerated
in
most
cases
can
be
easily
recovered
recycled,
revealing
high
sustainability
protocol.
Remarkably,
all
reactions
are
highly
efficient
furnish
excellent
yields
many
pure
products
were
obtained
just
by
washing
crude
reaction
mixture
pentane.
Significantly,
green
chemistry
metrics
found
excellent.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(12)
Published: Jan. 26, 2023
A
Pd-catalyzed
three-component
syn-1,2-arylmethylation
of
internal
alkynes
(ynamides/yne-acetates/alkynes)
is
described.
The
readily
available
and
bench
stable
coupling
partners
iodo-arenes,
methyl
boronic
acid
are
successfully
used
in
this
strategy
to
access
the
methyl-containing
tetra-substituted
olefins;
scope
broad
showing
excellent
functional-group
tolerance.
Notably,
transformation
regio-
as
well
stereoselective.
biologically
relevant
motifs
(BRM)
bearing
iodo-arenes
ynamides
also
for
late-stage
alkynes.
Aryl-alkylation,
aryl-trideuteriomethylation,
alkynyl-methylation,
alkenyl-methylation
presented.
Me-substituted
alkenes
further
transformed
into
synthetically
important
β-amino-indenones
α-fluoro-α'-methyl
ketones.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(7), P. 1524 - 1529
Published: Feb. 14, 2022
A
cationic
palladium-catalyzed
arylalkenylation
of
ynamides
is
presented.
The
putative
keteniminium
arylpalladium
intermediate
likely
dictates
the
regioselective
carbopalladation
ynamide
to
form
a
vinylpalladium
species.
capture
this
complex
by
olefin
yields
linear
conjugated
β-alkenyl
aminodienes
(especially
with
trans
selectivity).
transformation
features
broad
scope
labile
functional
group
tolerance
and
makes
42
unusual
molecular
scaffolds
structural
diversity.
DFT
studies
provide
valuable
insights
into
reaction
mechanism.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(7), P. 1233 - 1238
Published: March 2, 2022
Abstract
The
gold‐catalyzed
regioselective
formation
of
3‐hydroxyquinoline
is
accessed
by
combining
anthranils
and
alkynyl
sulfones.
selective
scission
the
epoxide
intermediate
stems
from
thermodynamic
stability
difference
resultant
cation
according
to
quantum
chemical
calculations.
subsequent
semi‐pinacol
rearrangement
leads
1,2‐shift
an
aryl
or
alkyl
group
originating
sulfone.
A
gram‐scale
synthesis
further
manifests
viability
protocol
for
preparation
this
important
scaffold.
magnified
image
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(14), P. 2428 - 2434
Published: July 3, 2023
Abstract
Gold‐catalyzed
interplay
between
ynamides
and
aminocarbonyls
comprises
a
route
to
2‐aminoquinolines.
This
modular
annulation
proceeds
under
relatively
mild
conditions
(Ph
3
PAuCl/AgNTf
2
5
mol
%,
DCE,
60–80
°C),
number
of
functionalities
were
compatible
(42
examples;
25–98%
yields).
In
contrast
group
other
gold‐catalyzed
methods
employing
the
ynamide/amine
combinations
for
assembly
2‐aminoquinolines,
developed
approach
utilizes
diversity
aminocarbonyl
substrates
and,
in
particular,
allows
variation
substituents
4
th
quinoline
position.
The
synthetic
potential
obtained
heterocyclic
products
was
illustrated
by
post‐modifications
backbone
peripheral
substituents.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(17), P. 3503 - 3508
Published: April 25, 2024
A
metal-free
TMSOTf-catalyzed
[4
+
2]
annulation
of
ynamides
with
β-(2-aminophenyl)-α,β-ynones
enables
the
regiospecific
and
facile
assembly
2-aminoquinoline
frameworks.
The
catalyst
TMSOTf
presented
a
remarkable
advancement
compared
to
previously
reported
transition-metal
catalysts.
wide
range
3-aryl/alkyl-substituted
2-aminoquinolines
were
generated
in
moderate
excellent
yields
due
mild
conditions.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 9, 2025
An
effective
strategy
to
synthesize
2,4-diaminoquinoline
compounds
has
been
efficaciously
developed
via
a
TMSOTf/TfOH-promoted
[4
+
2]
annulation
of
ynamides
with
2-aminoarylnitriles.
Compared
the
reported
transition-metal
catalysts,
this
metal-free
promotion
system
presented
remarkable
advancement,
enabling
facile
and
regiospecific
assembly
frameworks
wide
functional
group
compatibility
moderate
excellent
yields.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 12, 2025
2-Quinolones
represent
a
versatile
class
of
compounds
that
are
prevalent
in
natural
and
medicinally
relevant
molecules.
Here
we
report
new
approach
to
the
selective
formation
these
structures.
By
gold
catalysis,
range
benzaldehyde-tethered
ynamides
reacted
with
anilines,
leading
4-amino-3,4-dihydro-2-quinolones
high
efficiency
excellent
diastereoselectivity
dichloromethane.
Interestingly,
methyl
acetate
as
solvent,
same
reaction
produced
3-aryl
2-quinolones
major
products.
The
use
substoichiometric
amount
aniline
could
also
promote
this
transformation.