The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(15), P. 10551 - 10556
Published: July 17, 2024
Palladium-catalyzed
dipolar
cycloaddition
reactions
represent
an
efficient
strategy
for
the
construction
of
cyclic
compounds,
with
development
novel
precursors
being
a
key
focus.
In
this
study,
new
type
precursor
was
synthesized
through
assembly
vinylethylene
carbonate
unit
and
tetrahydronaphthalene
skeleton.
This
can
undergo
[3
+
2],
[5
4],
2]
reactions,
leading
to
tetrahydronaphthalene-fused
oxazolidin-2-ones,
1,5-oxazonines,
tetrahydrooxepines.
general,
all
these
exhibited
good
reaction
efficiency
functional
group
tolerance.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
The
cycloaddition
of
aziridines
with
unsaturated
compounds
is
a
valuable
method
for
synthesizing
nitrogen
heterocycles.
However,
this
process
predominantly
substrate-controlled,
posing
significant
challenges
in
regulating
the
regioselectivity
C–N
bond
cleavage.
In
study,
we
report
nickel-catalyzed
dynamic
kinetic
activation
strategy
that
enables
catalyst-controlled
aziridines.
Various
types
aziridines,
including
2-phenyl,
2-carbonyl,
2-alkyl,
and
disubstituted
consistently
cleave
their
more
sterically
hindered
bonds
to
generate
1,3-radical
anion
intermediates.
These
intermediates
participate
highly
regioselective
1,4-Heck/allylic
substitution
cascade
aromatic
branched
1,3-dienes,
resulting
radical-polar
crossover
(4
+
3)
produces
seven-membered
azepine
products.
This
approach
not
only
complements
traditional
dipolar
cycloaddition,
which
typically
act
as
zwitterionic
1,3-dipoles,
but
also
introduces
an
unusual
mode
1,3-dienes.
Experimental
investigations
density
functional
theory
(DFT)
calculations
provide
insight
into
reaction
mechanism.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(21), P. 4521 - 4527
Published: Aug. 7, 2024
Abstract
Catalyst‐controlled
switchable
(4+3)
and
(4+2)
annulation
reactions
of
Morita–Baylis–Hillman
carbonates
with
benzofuran‐derived
azadienes
have
been
established.
Employing
PCy
3
as
the
catalyst,
reaction
could
provide
a
variety
synthetically
useful
benzofuro[3,2‐
b
]azepines
in
good
yields
(80–92%)
excellent
chemo‐
regioselectivities
via
cycloaddition
reactions.
Whereas
changing
catalyst
from
to
DMAP,
were
switched
construct
highly
substituted
spirotetrahydroquinoline
scaffolds
three
sequential
stereocenters
containing
all‐carbon
spiro‐quaternary
efficiency
diastereoselectivities
(92–96%
all
cases>25:1
dr
)
annulations.
In
addition,
synthetic
utility
this
method
was
further
showcased
by
gram‐scale
transformations
product.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 18, 2024
Here,
we
report
a
novel
strategy
for
the
preparation
of
diverse
heterocycles
via
Pd-catalyzed
migratory
1,1-cycloannulation
reaction
(MCAR)
alkenes.
Starting
from
readily
available
alkenyl
amines
and
alcohols,
this
approach
allows
formation
wide
range
five-
to
seven-membered
azaheterocycles
oxaheterocycles
with
high
efficiency
good
functional
group
tolerance.
The
key
realization
is
use
4-iodophenol
or
2-iodophenol
derivatives
where
phenolic
hydroxyl
plays
critical
role
in
controlling
direction
migration
ring-size
through
quinone
methide
intermediate.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Multicomponent
reactions
are
an
efficient
and
widely
employed
synthetic
strategy,
known
for
their
capability
to
rapidly
effectively
construct
complex
molecular
architectures
from
multiple
starting
materials.
This
work
presents
a
chemo-
diastereoselective
three-component
reaction
the
1,3-difunctionalization
of
transient
carbonyl
ylides
with
H2O
azadienes,
facilitated
by
synergistic
catalysis
Rh2(OAc)4
phosphoric
acid.
strategy
provides
protocol
synthesis
highly
functionalized
dihydroisobenzofurans
in
high
yields
(up
94%)
good
diastereoselectivities
91:9
dr).
Additionally,
subsequent
transformations
nucleophiles
enable
structurally
diverse
compounds
enhanced
(dr
>95:5).
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 12, 2025
Herein,
we
report
a
gold(I)-catalyzed
heterocyclization/(5
+
3)
cycloaddition
cascade
of
yne-enones
with
imidazolidines,
providing
modular,
atom-economical
and
efficient
strategy
for
the
synthesis
cycloocta[c]furans
in
moderate
to
excellent
yields.
This
method
features
readily
available
substrates,
simple
operation,
mild
reaction
conditions,
broad
substrate
scope.
More
importantly,
asymmetric
version
is
also
achieved
by
employing
(R)-C2-TunePhos
ligand
(L7),
leading
optically
active
up
98:2
er.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(23), P. 4863 - 4867
Published: June 4, 2024
2,3-Indole-fused
1,4-diazocines
represent
a
new
family
of
indole
alkaloid
compounds
and
are
difficult
to
access
by
the
reported
protocols.
Herein,
we
report
copper-catalyzed
decarboxylative
cyclization
cyclic
propargylic
carbamates
with
imidazolidines
via
sequential
C-N/C-N/C-C
bond
formation
deliver
series
2,3-indole-fused
1,4-diazocines,
broad
substrate
scope
mild
conditions.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 26, 2024
Abstract
Cycloaddition
reactions
play
a
pivotal
role
in
synthetic
chemistry
for
the
direct
assembly
of
cyclic
architectures.
However,
hurdles
remain
extending
C4
synthon
to
construct
diverse
heterocycles
via
programmable
[4+n]-cycloaddition.
Here
we
report
an
atom-economic
and
modular
intermolecular
cycloaddition
using
furan-fused
cyclobutanones
(FCBs)
as
versatile
synthon.
In
contrast
well-documented
benzocyclobutenones,
this
is
complementary
version
FCB
reagent.
It
involves
C-C
bond
activation
sequence,
including
Rh-catalyzed
enantioselective
[4
+
2]-cycloaddition
with
imines
Au-catalyzed
diastereoselective
4]-cycloaddition
anthranils.
The
obtained
lactams,
which
are
motifs
that
present
many
natural
products,
bioactive
molecules,
materials,
inaccessible
or
difficult
prepare
by
other
methods.
Preliminary
antitumor
activity
study
indicates
6e
6
f
exhibit
high
anticancer
potency
against
colon
cancer
cells
(HCT-116,
IC
50
=
0.50
±
0.05
μM)
esophageal
squamous
cell
carcinoma
(KYSE-520,
0.89
0.13
μM),
respectively.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(22), P. 16736 - 16749
Published: Oct. 30, 2024
The
enantioselective
synthesis
of
eight-membered
cyclic
ether
has
always
been
a
challenge
in
organic
synthesis.
Herein,
we
reported
highly
tandem
cyclization
reaction
alkyne
ketone
and
dioxypyridines
mediated
by
chiral
bifunctional
catalysts.
This
generates
two
adjacent
stereocenters
using
an
atomeconomic
manner,
providing
simple
effective
method
for
the
one-step
ethers.
