Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(6), С. 1331 - 1340
Опубликована: Ноя. 14, 2023
Abstract
Herein
we
report
that
cycloheptatrienyl‐substituted
1,5‐diynes
with
aromatic
backbones
undergo
a
gold‐catalysed
5‐
endo
‐
dig
cyclisation
to
give
11
H
‐indeno‐[2,1‐
]azulenes
at
room
temperature.
This
methodology
complements
the
established
range
of
structures
obtained
from
conversions
differently
substituted
accessed
via
highly
reactive
cationic
intermediates.
We
have
demonstrated
scope
reaction
and
assessed
possibility
further
functionalisation
indenoazulene
scaffold.
Additionally,
studied
optical
electrochemical
properties
as
well
frontier
molecular
orbitals
this
structural
motif
by
both
spectroscopic
theoretical
means.
Chemical Science,
Год журнала:
2023,
Номер
14(13), С. 3493 - 3500
Опубликована: Янв. 1, 2023
A
copper-catalyzed
asymmetric
cascade
cyclization
via
C(sp
2
)–O
bond
cleavage
is
disclosed,
affording
a
range
of
chromeno[3,4-
c
]pyrroles
bearing
triaryl
oxa-quaternary
carbon
stereocenter
in
high
yields
and
enantioselectivities.
Chemical Science,
Год журнала:
2023,
Номер
14(22), С. 5918 - 5924
Опубликована: Янв. 1, 2023
Catalytic
enantioselective
transformation
of
alkynes
has
become
a
powerful
tool
for
the
synthesis
axially
chiral
molecules.
Most
these
atroposelective
reactions
rely
on
transition-metal
catalysis,
and
organocatalytic
approaches
are
largely
limited
to
special
which
act
as
precursors
Michael
acceptors.
Herein,
we
disclose
an
intramolecular
(4
+
2)
annulation
enals
with
ynamides.
This
method
allows
efficient
highly
atom-economical
preparation
various
7-aryl
indolines
in
generally
moderate
good
yields
excellent
enantioselectivities.
Computational
studies
were
carried
out
elucidate
origins
regioselectivity
enantioselectivity.
Furthermore,
phosphine
ligand
derived
from
synthesized
indoline
was
proven
be
potentially
applicable
asymmetric
catalysis.
One-carbon
ring
expansion
reaction
of
N-heterocycles
has
gained
particular
attention
in
the
past
decade
because
this
method
allows
for
conversion
readily
available
into
potentially
useful
complex
ring-expanded
N-heterocycles,
which
are
inaccessible
by
traditional
methods.
However,
catalytic
asymmetric
variant
been
rarely
reported
to
date.
Herein,
we
disclose
an
enantioselective
one-carbon
through
chiral
copper-catalyzed
diyne
cyclization,
leading
practical,
atom-economic
and
divergent
assembly
array
valuable
bearing
a
quaternary
stereocenter
generally
good
excellent
yields
with
enantioselectivities
(up
>99%
ee).
This
protocol
represents
first
example
based
on
alkynes.
Herein,
we
describe
an
efficient
copper-catalyzed
cyclization
of
triynes
via
vinyl
cation
intermediates.
The
reaction
leads
to
the
practical
and
atom-economical
synthesis
valuable
polycyclic
pyrroles
by
constructing
three
new
rings
in
one
step
under
mild
conditions.
proposed
mechanism
shows
ordered
regioselective
alkynes.
Moreover,
possibility
such
asymmetric
triyne
also
emerges.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 25, 2024
The
asymmetric
Büchner
reaction
and
related
arene
cyclopropanations
represent
one
type
of
the
powerful
methods
for
enantioselective
dearomatization.
However,
examples
reactions
via
a
non-diazo
approach
are
quite
scarce,
cyclopropanation
based
on
alkynes
has
not
been
reported.
Herein,
we
disclose
an
by
copper-catalyzed
controllable
cyclization
N-propargyl
ynamides
vinyl
cation
intermediates,
leading
to
chiral
tricycle-fused
cycloheptatrienes
benzonorcaradienes
in
high
yields
enantioselectivities.
Importantly,
this
protocol
represents
cations.
ACS Catalysis,
Год журнала:
2023,
Номер
13(13), С. 8803 - 8812
Опубликована: Июнь 19, 2023
Herein,
an
organocatalytic
enantioselective
desymmetrizing
hydroalkoxylation
of
1,4-
and
1,8-diynes
is
disclosed,
which
represents
a
unique
chiral
Brønsted
acid-catalyzed
desymmetrization
diynes.
This
protocol
provides
facile
practical
access
to
enantioenriched
1,3-diaminopropanol
derivatives
γ-butyrolactones
with
wide
substrate
scope
generally
high
enantioselectivities.
Besides,
the
backbones
these
products
constitute
structural
core
numerous
bioactive
molecules,
they
can
serve
as
valuable
precursors
for
expeditious
assembly
versatile
N-
O-heterocycles.
Moreover,
control
experiments
theoretical
calculations
are
employed
confirm
mechanistic
rationale
elucidate
origin
enantioinduction.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(8)
Опубликована: Дек. 27, 2022
Herein,
an
I2
-catalyzed
unprecedented
cycloisomerization
of
ynamides
is
developed,
furnishing
various
functionalized
bis(indole)
derivatives
in
generally
good
to
excellent
yields
with
wide
substrate
scope
and
atom-economy.
This
protocol
not
only
represents
the
first
molecular-iodine-catalyzed
tandem
complex
alkyne
cycloisomerizations,
but
also
constitutes
chemoselective
tryptamine-ynamides
involving
distinctively
different
C(sp3
)-C(sp3
)
bond
cleavage
rearrangement.
Moreover,
chiral
tetrahydropyridine
frameworks
containing
two
stereocenters
are
obtained
moderate
diastereoselectivities
enantioselectivities.
Meanwhile,
aromatization
produce
pyrrolyl
indoles
high
efficiency
enabled
by
.
Additionally,
control
experiments
theoretical
calculations
reveal
that
this
reaction
probably
undergoes
a
5-exo-dig
cyclization/rearrangement
process.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
10(1), С. 203 - 208
Опубликована: Ноя. 24, 2022
An
efficient
copper-catalyzed
formal
[4
+
1]
annulation
of
N
-propargyl
ynamides
with
diketones
has
been
developed,
allowing
practical
and
atom-economic
synthesis
valuable
pyrrole-substituted
dioxoles
in
generally
moderate
to
excellent
yields.
