Research Square (Research Square),
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 19, 2024
Abstract
The
activation
of
C−C
bond
benzocyclobutenones
under
mild
reaction
conditions
remains
a
challenge.
We
herein
report
photoinduced
catalyst-free
regio-specific
C1−C8
cleavage
benzocyclobutenones,
enabling
the
generation
versatile
ortho-quinoid
ketene
methides
for
aza-[4
+
2]-cycloaddition
with
imines,
which
offers
facile
route
to
isoquinolinone
derivatives,
including
seven
family
members
protoberberine
alkaloids,
gusanlung
A,
B,
D,
8-oxotetrahydroplamatine,
tetrahydrothalifendine,
tetrahydropalmatine,
and
xylopinine.
Furthermore,
catalytic
enantioselective
version
this
strategy
was
realized
by
merging
synergistic
photocatalysis
chiral
Lewis
acid
catalysis.
Mechanistic
studies
provided
compelling
evidence
rationalize
photoisomerization/cycloaddition
cascade
process.
Chemical Science,
Год журнала:
2024,
Номер
15(39), С. 16050 - 16058
Опубликована: Янв. 1, 2024
We
have
synthesized
β-diaryl-β-hydroxyl-α-amino
acid
derivatives
through
radical
addition-type
aldol
reaction,
which
was
confirmed
by
spectroscopic
experiments,
control
and
DFT
calculations.
Organic Letters,
Год журнала:
2025,
Номер
27(4), С. 1006 - 1011
Опубликована: Янв. 16, 2025
Herein,
we
introduce
a
scandium-catalyzed
synthetic
strategy
that
provides
access
to
diverse
and
functionalized
array
of
cyclobutene
frameworks
adorned
with
quaternary
carbon
center.
This
approach
broadens
the
repertoire
2-alkynylnaphthols
alkenes,
offering
versatile
platform
for
construction
complex
molecular
architectures.
The
asymmetric
catalytic
[2
+
2]
cycloaddition
reaction
demonstrates
wide
substrate
scope
an
impressive
functional
group
tolerance,
yielding
products
high
efficiency,
up
97%
yield,
excellent
enantiomeric
excess
97%.
simplicity
scaling
this
process,
coupled
ease
converting
these
into
variety
substituted
products,
significantly
enhances
utility
method.
Abstract
Catalytic
asymmetric
dearomatization
reactions
represent
a
versatile
platform
for
constructing
complex
optically
active
three-dimensional
molecules.
We
present
visible-light-induced
dearomative
[2+2]
cycloaddition/ring-expansion
reaction
of
indole
derivatives
with
simple
alkenes
in
the
presence
chiral
N,N′-dioxide/terbium
complex.
This
strategy
provides
access
to
range
valuable
cyclopenta[b]indoles,
and
its
synthetic
potential
is
further
showcased
through
gram-scale
synthesis,
bioactivity
against
human
breast
cancer,
transformation
into
yuehchukene
analogue.
A
series
control
spectral
experiments,
as
well
DFT
calculations,
provide
compelling
evidence
elucidate
mechanism.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
A
mild
CuI-catalyzed
dearomatization/peroxidation/cyclization
cascade
of
pyrrole-tethered
indoles
has
been
reached,
providing
peroxide-incorporated
indolizino[8,7-b]indole
derivatives
in
acceptable
to
good
yields
(46–76%).
Dehydrogenated
peroxide
can
be
obtained
by
the
use
a
FeCl3/TBHP
(tBuOOH)/2,2,2-trifluoroethanol
(TFE)
system
at
50
°C.
The
enantioselective
formal
(3
+
2)
cyclization
and
sequential
reaction
of
2-malononitrile-substituted
oxindoles
with
benzaldehydes
ortho-aminobenzaldehydes
were
achieved
by
chiral
N,N′-dioxide/metal
complex
Lewis
acid
catalysts.
This
protocol
supplies
facile
efficient
access
to
highly
functionalized
dihydrofuran-
azepine-based
spirooxindoles.
Based
on
the
control
experiments
deuterium
labeling
studies,
interconversion
diastereomeric
intermediates
under
conditions
reversible
1,5-H
transfer
step
disclosed.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 8, 2025
Enzymatic
catalysis
in
biological
systems
is
characterized
by
the
specific
pocket
confinement
imposed
various
protein
matrixes,
enabling
synthesis
of
a
diverse
array
functional
biomolecules.
Development
new
catalysts
that
incorporate
multiple
catalytic
centers
within
enzyme-mimic
confined
spaces
presents
meaningful
yet
challenging
project
for
synthetic
chemists.
Here,
we
present
our
recent
achievement
synthesizing
chiral
photosensitive
metal-organic
cage
(cPMOC),
Δ4-/Λ4-MOC-68-Ru4,
which
possesses
pockets
can
facilitate
visible-light-induced
asymmetric
cascade
intermolecular
[2
+
2]
cycloaddition/acyloin
rearrangement
first
time.
The
current
photochemical
transformation
affords
bicyclo[3.2.1]octanes
with
opposite
regiospecificity
contrast
to
well-established
thermodynamically
favored
[3
cycloaddition
transformations
similar
reaction
counterparts.
distinctive
size
2
inhibits
dimerization
α,β-unsaturated
ketones
and
promotes
heterocycloaddition
between
ketone
smaller
cyclic
1,2-dione,
underscoring
critical
role
microenvironmental
shape
guest
binding
determining
reactivity.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Дек. 30, 2024
The
activation
of
C-C
bond
benzocyclobutenones
under
mild
reaction
conditions
remains
a
challenge.
We
herein
report
photoinduced
catalyst-free
regio-specific
C1-C8
cleavage
benzocyclobutenones,
enabling
the
generation
versatile
ortho-quinoid
ketene
methides
for
aza-[4
+
2]-cycloaddition
with
imines,
which
offers
facile
route
to
isoquinolinone
derivatives,
including
seven
family
members
protoberberine
alkaloids,
gusanlung
A,
B,
D,
8-oxotetrahydroplamatine,
tetrahydrothalifendine,
tetrahydropalmatine,
and
xylopinine.
Furthermore,
catalytic
enantioselective
version
this
strategy
is
also
realized
by
merging
synergistic
photocatalysis
chiral
Lewis
acid
catalysis.
Mechanistic
studies
provide
compelling
evidence
rationalize
photoisomerization/cycloaddition
cascade
process.
