The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(11), С. 7490 - 7499
Опубликована: Май 18, 2021
A
novel
Brønsted
acid
catalyzed
1,8-addition
mediated
(3
+
4)-annulation
of
in
situ
generated
propargylic
p-quinone
methides
with
2-indolylmethanols
is
described.
This
method
provides
a
convenient
and
mild
approach
to
structurally
interesting
synthetically
important
polysubstituted
indole-fused
oxepines
high
yields.
Moreover,
as
four-atom
synthons
the
4)-annulations
under
conditions
have
been
explored
for
first
time.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(39), С. 17049 - 17054
Опубликована: Июнь 18, 2020
An
organocatalytic
enantioconvergent
synthesis
of
chiral
tetrasubstituted
allenes
is
disclosed.
With
suitable
phosphoric
acid
catalysts,
a
range
racemic
indole-substituted
propargylic
alcohols
reacted
with
nucleophiles
to
provide
efficient
access
series
enantioenriched
high
enantioselectivities.
Control
experiments
suggested
mechanism
involving
remotely
controlled
asymmetric
1,8-addition
the
in
situ
generated
indole
imine
methide
via
bifunctional
transition
state.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
143(2), С. 604 - 611
Опубликована: Дек. 31, 2020
Arene
dearomatization
is
a
straightforward
method
for
converting
an
aromatic
feedstock
into
functionalized
carbocycles.
Enantioselective
dearomatizations
of
chemically
inert
arenes,
however,
are
quite
limited
and
underexplored
relative
to
those
phenols
indoles.
We
developed
diazo-free
generation
silver-carbene
species
from
ynamide
applied
it
the
nonactivated
arenes.
Transiently
generated
norcaradiene
could
be
trapped
by
intermolecular
[4
+
2]
cycloaddition,
synthesizing
polycycles
with
five
consecutive
stereogenic
centers.
This
protocol
constitutes
first
highly
enantioselective
reaction
based
on
species.
Mechanistic
investigations
revealed
followed
two
different
classes
pericyclic
reactions,
as
well
origin
chemo-
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27164 - 27170
Опубликована: Окт. 21, 2021
Described
herein
is
a
novel
Brønsted
acid
catalyzed
intramolecular
hydroalkoxylation/Claisen
rearrangement,
allowing
the
practical
and
atom-economic
synthesis
of
range
valuable
spirolactams
from
readily
available
ynamides
in
generally
good
to
excellent
yields
with
diastereoselectivities
broad
substrate
scope.
Importantly,
an
unexpected
dearomatization
nonactivated
arenes
heteroaromatic
compounds
involved
this
tandem
sequence.
Moreover,
asymmetric
version
cyclization
was
also
achieved
by
efficient
kinetic
resolution
chiral
phosphoric
catalysis.
In
addition,
[3,3]-rearrangement
shown
be
kinetically
preferred
over
related
[1,3]-rearrangement
theoretical
calculations.
Fundamental Research,
Год журнала:
2022,
Номер
3(2), С. 237 - 248
Опубликована: Янв. 21, 2022
The
catalytic
asymmetric
construction
of
axially
chiral
indole-based
frameworks
is
an
important
area
research
due
to
the
unique
characteristics
such
frameworks.
Nevertheless,
in
this
still
its
infancy
and
has
some
challenges,
as
designing
constructing
new
classes
scaffolds
developing
their
applications
catalysts,
ligands,
etc.
To
overcome
these
we
present
herein
design
atroposelective
synthesis
aryl-pyrroloindoles
a
class
via
strategy
organocatalytic
(2
+
3)
cyclization
between
3-arylindoles
propargylic
alcohols.
More
importantly,
was
derived
into
phosphines,
which
served
efficient
ligands
palladium-catalyzed
reactions.
Moreover,
theoretical
calculations
provided
in-depth
understanding
reaction
mechanism.
This
work
offers
for
scaffolds,
are
promising
finding
more
catalysis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9244 - 9253
Опубликована: Июнь 3, 2024
Catalytic
asymmetric
dearomatization
(CADA)
is
a
powerful
tool
for
the
rapid
construction
of
complex
chiral
three-dimensional
cyclic
molecules
featuring
quaternary
carbon
centers
from
readily
available
arenes.
However,
ubiquitous
nonfunctionalized
1-naphthols
to
afford
remains
challenging
and
undeveloped.
This
study
reports
dearomative
[4
+
1]
spiroannulation
via
copper
catalysis.
reaction
features
highly
chemo-,
regio-,
stereoselective
nucleophilic
addition
intramolecular
annulation
cascade
reactive
π-extended
copper-allenylidene,
thus
enabling
practical
synthesis
range
valuable
spirocyclic
enones
bearing
stereocenter
with
high
efficiency.
Furthermore,
this
protocol
applicable
phenols.
Control
experiments
supported
substitution-annulation
mechanism
by
excluding
process
involving
1,3-sigmatropic
shift.
Preliminary
biological
activity
studies
indicated
that
synthesized
hold
significant
promise
as
anticancer
agents
inducing
tumor
cell
apoptosis.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(5), С. 1234 - 1240
Опубликована: Янв. 1, 2022
Chiral
phosphoric
acid
has
been
utilized
for
covalent
activation
of
propargylic
alcohols
to
act
as
pre-catalyst.
With
this
mode,
a
range
highly
regio-
and
enantioenriched
heterocyclic
products
could
be
generated
efficiently
from
racemic
alcohols.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
88(12), С. 7684 - 7702
Опубликована: Ноя. 23, 2022
An
axially
chiral
indolyl-pyrroloindole
scaffold,
a
new
member
of
indole-based
scaffolds,
has
been
designed,
and
the
catalytic
asymmetric
construction
this
scaffold
established
by
strategy
organocatalytic
(2
+
3)
cycloaddition
3,3'-bisindoles
with
isoindolinone-based
propargylic
alcohols.
By
approach,
series
derivatives
bearing
both
axial
chirality
central
were
synthesized
in
high
yields
excellent
diastereo-
enantioselectivities
(up
to
95%
yield,
91:9
dr,
99%
ee).
This
reaction
not
only
realizes
first
n)
as
1,2-dinucleophiles
but
also
provides
for
atroposelective
scaffolds
five-five-membered
rings,
thus
solving
challenges
constructing
class
scaffolds.
Organic Letters,
Год журнала:
2022,
Номер
24(27), С. 4914 - 4918
Опубликована: Июнь 30, 2022
An
asymmetric
organocatalytic
remote
1,10-addition
of
alkynyl
indole
imine
methides
generated
in
situ
from
α-(6-indolyl)
propargylic
alcohols
with
thiazolones
has
been
developed
for
the
first
time,
affording
axially
chiral
tetrasubstituted
allenes
featuring
vicinal
sulfur-containing
quaternary
carbon
stereocenters
high
yields
excellent
stereoselectivities.
The
representative
scale-up
reaction
and
transformations
1,10-adduct
were
examined.
mechanism
was
expounded
by
control
experiments
DFT
calculations.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(9), С. 1332 - 1384
Опубликована: Март 14, 2023
Abstract
Conjugated
and
non‐conjugated
allenones
appear
as
recurring
motifs
in
organic
synthesis,
natural
products
mechanistic
investigations
showing
unique
properties
applications.
The
ability
of
to
build
cycles
has
provided
a
direct
access
strained
systems,
medium‐sized
rings,
arenes,
heterocycles
complex
polycycles.
In
addition,
have
served
models
catalysis.
critic
compilation
herein
presented
will
provide
an
exhaustive
overview
the
synthetic
possibilities
may
offer,
which
certainly
inspire
our
community
their
search
more
efficient
methodologies,
preparation
biological
pharmaceutical
targets,
improve
knowledge
theoretical
chemistry.
Great
part
this
review
discuss
aspects,
catalysis
innovation
insights
chemical
transformations
implying
allenone
motif.
many
examples
on
total
synthesis
pharmacologically
active
compounds
be
described.
We
hope
that
attractive
chemistry,
catalysis,
medicinal
chemistry
communities.
magnified
image
