Lewis Acid-Enabled Chemodivergent Cycloadditions of Donor–Acceptor Cyclopropanes with Indoline-2-Thiones
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 20, 2025
Lewis
acid-enabled
reactions
of
donor-acceptor
cyclopropanes
(DACs)
with
indoline-2-thiones
are
reported.
The
reaction
exhibits
tunable
annulation
depending
on
the
acid
and
substituent
at
N1
indoline-2-thiones.
With
AlCl3
as
1-isopropylindoline-2-thiones
reactants,
a
direct
ring
opening
DACs,
followed
by
intramolecular
nucleophilic
addition/dehydration
takes
place
leading
to
formation
dihydro-2H-thiepino[2,3-b]indoles
in
moderate
good
yields.
Using
Yb(OTf)3
promoter
1-unsubstituted
(3
+
2)
cycloaddition
DACs
accompanied
sulfur
rearrangement
give
3-indolyl-4,5-dihydrothiophenes
In
addition,
synthetic
transformation
3-indolyl-4,5-dihydrothiophene
sulfone
indole-based
axially
chiral
scaffolds
further
extends
utility
structural
complexity.
Язык: Английский
P(═O)R2-Directed Asymmetric Catalytic C–H Olefination Leading to C–N Axially Chiral Targets
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
A
novel
P(═O)R2-directed
asymmetric
catalytic
olefination
has
been
developed,
enabling
efficient
access
to
carbon–nitrogen
axially
chiral
products
with
excellent
yields
(up
92%)
and
enantioselectivity
99%
enantiomeric
excess).
The
synergistic
coordination
of
phosphine
oxide
functionality
l-pGlu-OH
the
Pd
metal
center,
serving
as
an
directing
group
ligand,
was
key
success
this
C–H
functionalization
system.
reaction
demonstrated
a
broad
substrate
scope,
yielding
33
distinct
C–N
axial
products.
absolute
configuration
unambiguously
confirmed
via
X-ray
diffraction
analysis.
Additionally,
three
representative
applications
were
showcased,
involving
reduction
oxidation
produce
phosphines
related
derivatives.
plausible
cycle
mechanism
proposed,
supported
by
detailed
experimental
studies.
Aggregates
in
system
identified
aggregation-induced
polarization
experiments.
Язык: Английский
Palladium-Catalyzed (3 + 2) Annulation of Azaborines with Vinyl Epoxides for Constructing Polycyclic Oxazaborolidines
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 25, 2025
A
palladium-catalyzed
(3
+
2)
annulation
of
azaborines
with
vinyl
epoxides
has
been
established.
By
this
strategy,
various
polycyclic
oxazaborolidines
structural
diversity
were
synthesized
in
generally
high
yields
(up
to
99%).
The
can
be
scaled
up
and
the
further
functionalized
through
olefin
metathesis
Heck
reaction,
which
demonstrated
good
feasibility
for
downstream
transformations.
Moreover,
catalytic
asymmetric
version
accomplished
under
catalysis
palladium/chiral
phosphoramidite
ligand,
producing
chiral
overall
enantioselectivities
98:2
er).
This
work
not
only
represents
first
1,2-azaborines
but
also
offers
an
efficient
strategy
constructing
benzooxazaborolidine
skeletons,
particularly
those
enantioenriched
fashion.
Язык: Английский
Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 5, 2025
Photoredox
catalysis
has
emerged
as
a
powerful
tool
for
forming
and
breaking
chemical
bonds,
further
taking
hold
with
its
integration
asymmetric
catalysis.
While
the
dual-catalytic
approach
led
to
successful
examples
of
control
stereogenic
centers,
axes
remained
underexplored.
In
this
study,
an
acylimine
intermediate
was
generated
through
photoredox
catalysis,
symmetric
substrate,
2-arylresorcinol,
desymmetrized
aid
chiral
phosphoric
acid
Using
approach,
center
axis
were
successfully
controlled
provide
natural-product-driven
compound.
The
origins
enantioselectivity
diastereoselectivity
investigated
density
functional
theory
study
four
possible
enantiodetermining
transition
states.
Consequently,
first
total
syntheses
ring-contracted
naphthylisoquinoline
alkaloid
ancistrobrevolines
A
B
accomplished
concisely.
This
provides
not
only
novel
methodology
strategy
synthesize
alkaloids
but
also
direction
advance
catalytic
research
synthesis
studies.
Язык: Английский
Enantioselective Synthesis of Benzodihydrofurans Bearing Axial and Central Stereogenic Elements
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(69)
Опубликована: Сен. 27, 2024
Abstract
The
enantioselective
synthesis
of
chiral
compounds
containing
multiple
stereogenic
elements
via
a
single
catalytic
step
is
challenging
process.
In
the
presence
α‐chloronitrostyrenes
and
squaramide
catalyst,
C−C
or
C−N
pro‐axially
2‐naphthol
substrates,
featuring
low
barriers
to
enantiomerization,
underwent
remote
diastereo‐
domino
Michael/
O
‐alkylation.
It
provided
desired
benzodihydrofurans
bearing
two
carbon
atoms
configurationally
stable
bond,
thanks
high
increase
barrier
rotation
upon
dihydrofurannulation.
Язык: Английский
Bro̷nsted Acid-Catalyzed Regioselective [5 + 1] Annulation for the Synthesis of Indole-Fused Dihydrochromanes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(22), С. 16791 - 16803
Опубликована: Ноя. 3, 2024
A
Bro̷nsted
acid-catalyzed
[5
+
1]
annulation
of
2-(1
Язык: Английский
Site-Selective Electrophilic Trifluoromethylthiolation for the Synthesis of C5- or C7-SCF3-Substituted Indolines
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
We
report
herein
an
efficient
and
site-selective
electrophilic
trifluoromethylthiolation
of
indolines.
In
the
absence
any
catalyst
or
additive,
C5-selective
could
proceed
at
room
temperature.
With
palladium
used
as
catalyst,
selectivity
was
reversed
completely,
giving
C7-selecive
trifluoromethylthiolated
products.
This
reaction
features
good
functional
group
tolerance,
simple
operation,
mild
conditions,
scale-up
application.
The
potential
utilities
products
were
shown
by
further
transformations.
Язык: Английский
Chiral Phosphoric Acid-Catalyzed Enantioselective Synthesis of 2,2-Disubstituted 2,3-Dihydro-4-quinolones from Isatins and 2′-Aminoacetophenones
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 24, 2024
Herein,
we
present
the
enantioselective
synthesis
of
2,3-dihydro-4-quinolones
bearing
chiral
tetrasubstituted
carbons
from
isatins
and
2′-aminoacetophenones.
The
transformation
is
mediated
by
a
phosphoric
acid
catalyst
proceeds
via
an
in
situ
generated
ketimine
subsequent
intramolecular
cyclization.
methodology
features
broad
scope
functional
group
tolerance
with
yields
enantioselectivities
up
to
99%
98%
ee.
Detailed
density
theory
(DFT)
calculations
support
proposed
reaction
mechanism
origin
asymmetric
induction.
Язык: Английский
Photo-Promoted Construction of 3-Spiro-2-sulfonylimino-indoline Skeletons via Cascade Reaction
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 25, 2024
The
cascade
reaction
of
3-diazo-2-sulfonyliminoindolines
and
N-methoxymethyl-N-[(trimethylsilyl)methyl]benzylamines
generates
2-sulfonylimino-1′,3′,4′,6′-tetrahydro-2'H-spiro[indoline-3,5′-pyrimidine]
spiro[indoline-3,3′-pyrrolidine]
derivatives
simultaneously
under
the
catalysis
TFA
blue
light
irradiation.
Their
formation
mechanisms
were
proposed
on
basis
isotope-labeled
experiments
HRMS
analysis
controlled
experiment
mixture,
showing
new
pathways.
current
provides
a
strategy
for
synthesis
biologically
important
spiro[indoline-3,3′-pyrrolidine]-2-one
derivatives.
Язык: Английский