RSC Advances,
Journal Year:
2022,
Volume and Issue:
12(42), P. 27483 - 27491
Published: Jan. 1, 2022
Density
functional
theory
(DFT)
calculations
have
been
performed
to
reveal
the
mechanism
of
gold(i)-catalyzed
annulation
N-allylynamides
and
benzofuroxans
as
nitrene
transfer
reagents
construct
azaheterocyclic
compounds.
The
calculated
results
revealed
that
reaction
mainly
undergoes
eight
processes.
Among
steps,
intramolecular
nucleophilic
attack
imino
N
atom
on
α-position
activated
gold
keteniminium
is
a
rate-determining
process,
which
different
from
proposed
previously
by
experiment.
chemoselectivity
products
controlled
competition
between
cyclopropanation
α-imino
carbenes
phenyl
ring
carbenes,
could
be
explained
NPA
charge.
yields
cyclopropanated
product
in
solvents
are
dictated
relative
polarity
leading
energy
barriers
steps.
present
work
expounds
experimental
observation
at
molecular
level
informative
for
exploring
efficient
syntheses
3-azabicyclo[3.1.0]hexanes.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
summarizes
the
latest
trends
and
developments
of
isoxazole-enabled
alkyne
amination
reactions
their
applications
in
divergent
heterocycle
synthesis.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(39), P. 7101 - 7106
Published: Sept. 22, 2022
Multisubstituted
alkenes
are
accessible
by
a
gold-catalyzed
acyloxyalkynylation
of
ynamides
with
ethynylbenziodoxolones
(EBXs)
perfect
atom-economy.
The
EBX
reagents
transfer
both
the
carboxylate
as
well
alkynyl
entity.
Overall,
this
cascade
comprises
in
situ
generation
an
gold(III)
species,
stereoselective
C(sp)-C(sp2)
bond
formation,
and
C-O
coupling
at
position
ynamides.
This
reaction
proceeds
under
mild
conditions
accepts
wide
range
substrates.
A
number
tetrasubstituted
amide
enol
2-iodobenzoates
bearing
different
functional
groups
were
obtained
good
to
excellent
yields.
DFT
calculations
explain
observed
regioselectivity.
synthetic
potential
was
further
demonstrated
selected
follow-up
transformations.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(21), P. 3697 - 3707
Published: Sept. 24, 2022
Abstract
The
gold‐catalyzed
annulation
of
alkynylsulfones,
involving
pyridine
N
‐oxides
(as
O
‐atom
transfer
reagents)
and
nitriles
C=N
synthons),
comprises
a
diazo‐free
route
to
valuable
4‐sulfonyl‐1,3‐oxazoles.
This
reaction
operates
under
relatively
mild
conditions
(IPrAuNTf
2
5
mol
%,
rt
or
60
°C),
number
functionalities
was
compatible
(35
examples;
14–95%).
In
most
cases,
the
SO
fragment,
which
is
typically
expulsed
in
previously
reported
Au‐catalyzed
‐transfers
retains
heterocyclic
products.
postulated
mechanism
suggests
key
role
reactive
gold
α‐oxo
carbene
intermediates
formed
via
transfer.
magnified
image
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(48), P. 8756 - 8760
Published: Nov. 28, 2023
Gold(III)-catalyzed
annulation
of
electron-deficient
alkynes
and
2-amino-arylcarbonyls
provides
general
modular
one-step
access
to
a
broad
scope
quinoline
products.
This
highly
selective
reaction
is
useful
alternative
the
classic
Friedländer
synthesis,
which
requires
harsh
conditions.
In
contrast,
developed
method
works
under
relatively
mild
PicAuCl2-catalyzed
conditions
exhibits
high
functional
group
tolerance
(40
examples;
yields
≤96%).
Another
feature
approach
versatility
toward
other
alkynes.
Alkynylsulfones,
alkynylcarbonyls,
alkynylphosphonates,
propiolonitriles,
trifluoromethylated
can
be
used
as
starting
materials
for
preparation
quinolines
diversely
substituted
at
position
3.
On
basis
experimental
data,
we
proposed
mechanism
in
gold(III)
functions
strong
electrophilic
activator
C≡C
bond
carbonyl
group.
The
synthetic
potential
presented
additionally
illustrated
by
practical
postmodifications
obtained
compounds,
including
two-step
synthesis
interpirdine,
potent
drug
candidate.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(9), P. 2079 - 2089
Published: March 2, 2024
Abstract
α‐Indol‐3‐yl
α,β‐unsaturated
carbonyl
compounds
are
synthesized
from
3‐propargyl
indoles,
obtained
by
direct
propargylation
of
via
a
gold‐catalyzed
tandem
oxidation‐1,2‐indole
migration
reaction
in
the
presence
pyridine
N
‐oxides.
Fine‐tuning
catalyst
and
oxidant
enables
indoles
bearing
different
substituents.
The
order
oxidation
indole
is
determined
terminal
or
internal
nature
alkyne
moiety.
In
addition,
process
can
be
coupled
with
additional
reactions,
allowing
an
increase
molecular
complexity
design
more
elaborated
reactions.
this
sense,
derivatives
alkenyl
substituent
at
position
evolve
through
migration‐Nazarov
cyclization
producing
α‐indolyl
cyclopentenones.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 31, 2024
Abstract
A
new
strategy
for
thiochromen‐4‐one
synthesis
that
relies
on
the
denitrative
formal
[5+1]
cycloaddition
of
1‐(2‐nitrophenyl)‐2‐yn‐1‐ones
with
thioacetamide
is
described.
Achieved
under
reaction
conditions
did
not
require
transition
metal
catalysis,
nor
exclusion
air
or
moisture,
suggested
to
involve
exploiting
propensity
undergo
hydrolysis
basic
conditions.
This
follows
by
addition
ensuing
sulfide
anion
1,3‐alkynone
and
a
nucleophilic
aromatic
substitution
rearomatization
cascade
give
S
‐heterocyclic
product
in
yields
41–99
%.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(9), P. 6274 - 6280
Published: April 20, 2024
Herein,
a
one-pot
desulfonylative
protocol
enabled
by
copper(II)/zinc(II)
salts
to
access
pyrrolo[2,3-b]quinolines
in
good
excellent
yields
from
2-carbonylanilines
and
ynamide-derived
buta-1,3-diynes
has
been
reported.
Significantly,
various
carrying
reactive
functional
groups
are
well
tolerated.
Moreover,
gram-scale
synthesis
synthetic
application
highlight
the
practical
utility
of
current
protocol.
Notably,
fluorescence
properties
have
recorded,
their
potential
use
as
fluorescent
probe
imaging
live
cells
demonstrated.
