Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(15), P. 3769 - 3774
Published: July 3, 2021
Abstract
A
gold‐catalyzed
cyclization/cascade
skeletal
rearrangement
of
o
‐cyanophenylalkynones
with
3‐amino‐benzo[
d
]‐isoxazoles
has
been
developed,
which
provides
an
approach
for
synthesizing
medium‐sized
benzolactones.
Based
on
the
experimental
results,
we
postulate
that
initial
nucleophilic
attack
occurs
preferentially
at
keto
moiety
instead
gold‐carbene.
This
reactivity
initiates
attractive
cascade
process
involving
carbene
transfer,
1,2‐aryl
migration,
cycloaddition,
ring‐expansion
etc.
resulting
in
multiple
bonds
cleavage
substrates.
magnified
image
Advanced Synthesis & Catalysis,
Journal Year:
2019,
Volume and Issue:
362(4), P. 755 - 759
Published: Nov. 13, 2019
Abstract
A
vinyl/
α
‐oxo
carbene
is
generated
via
an
formation
and
subsequently
transferred
across
the
second
alkyne.
These
highly
active
species
can
react
with
nitriles
in
intermolecular
fashion
to
provide
substituted
oxazoles.
This
methodology
goes
through
1,6‐carbene
shift
offers
a
range
of
valuable
products.
magnified
image
Chemistry - A European Journal,
Journal Year:
2019,
Volume and Issue:
26(16), P. 3600 - 3608
Published: Dec. 18, 2019
This
work
reports
gold-catalyzed
iminations
of
terminal
propargyl
alcohols
with
anthranils
or
isoxazoles
to
yield
E-configured
α-amino-2-en-1-ones
and
-1-als
complete
chemoselectivity.
These
catalytic
occur
exclusively
C(1)-nucleophilic
additions
on
alkynes,
in
contrast
a
typical
C(2)-route.
For
3,3-dialkylprop-1-yn-3-ols,
methyl
substituent
is
superior
long
alkyl
chains
as
the
1,2-migration
groups
toward
α-imino
gold
carbenes.
secondary
prop-1-yn-3-ols,
phenyl,
vinyl,
cyclopropyl
substituents
are
better
than
hydrogen
migrating
groups,
obviating
carbene
reactions.
DFT
calculations
have
been
performed
rationalize
observed
C(1)-regioselectivity
preferable
migration
based
pathways.
The Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
86(18), P. 12964 - 12972
Published: Sept. 2, 2021
The
gold-catalyzed
reaction
between
benzofuroxans,
functioning
as
nitrene
transfer
reagents,
and
N-allylynamides
leads
to
3-azabicyclo[3.1.0]hexan-2-imines.
This
highly
selective
annulation
proceeds
smoothly
under
mild
conditions
(5
mol
%
Ph3PAuNTf2,
PhCl,
60
°C)
exhibits
high
functional
group
tolerance
(21
examples,
≤96%
yields).
obtained
cyclopropanated
products
represent
a
useful
synthetic
platform
with
an
easily
modulated
substitution
pattern
illustrated
by
their
postmodifications.
Intramolecular
cyclopropanation
of
gold
α-imino
carbene
intermediates
is
suggested
key
step
the
catalytic
cycle.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(15), P. 3769 - 3774
Published: July 3, 2021
Abstract
A
gold‐catalyzed
cyclization/cascade
skeletal
rearrangement
of
o
‐cyanophenylalkynones
with
3‐amino‐benzo[
d
]‐isoxazoles
has
been
developed,
which
provides
an
approach
for
synthesizing
medium‐sized
benzolactones.
Based
on
the
experimental
results,
we
postulate
that
initial
nucleophilic
attack
occurs
preferentially
at
keto
moiety
instead
gold‐carbene.
This
reactivity
initiates
attractive
cascade
process
involving
carbene
transfer,
1,2‐aryl
migration,
cycloaddition,
ring‐expansion
etc.
resulting
in
multiple
bonds
cleavage
substrates.
magnified
image
