Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(39)
Published: June 25, 2024
Abstract
The
design
of
various
cycloaddition/annulation
processes
is
one
the
most
intriguing
challenges
in
development
donor‐acceptor
(D–A)
cyclopropane
chemistry.
In
this
work,
a
new
class
formal
high‐order
[6+n]‐cycloaddition
and
annulation
D–A
cyclopropanes
with
cycloheptatriene
systems
has
been
designed
reported,
to
fill
significant
gap
chemistry
cyclopropanes.
reactivity
methylated
cycloheptatrienes
from
Me1
Me5
as
well
unsubstituted
was
studied
detail
under
GaCl
3
activation
conditions,
which
makes
it
possible
efficiently
generate
gallium
1,2‐zwitterionic
complexes
or
1,3‐zwitterionic
intermediates
starting
cyclopropanes,
while
other
Lewis
acids
are
ineffective
non‐selective.
New
examples
[6+2]‐,
[6+3]‐,
[6+4]‐,
[6+1]‐,
[4+2]‐cycloaddition
reactions
along
more
complex
were
discovered.
Cycloheptatriene
itself
can
also
successfully
act
hydride
anion
donor,
allows
ionic
hydrogenation
be
performed
mild
conditions.
As
result,
number
efficient
highly
diastereoselective
protocols
for
synthesis
seven‐membered
carbocycles
developed.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(13), P. 4797 - 4803
Published: Jan. 1, 2024
A
highly
enantioselective
[4
+
2]
cycloaddition
of
a
number
simple
olefins
with
cyclic
hetero-diene
dioxopyrrolidines
is
realized
by
chiral
iron(
iii
)/
N
,
′-dioxide
complex
catalyst.
European Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Abstract
This
review
collects
the
recent
developments
in
synthesis
of
chiral
heterocycles
through
enantioselective
silver‐catalyzed
transformations
published
since
2018.
It
demonstrates
power
silver
catalysts
as
special
mild
Lewis
acids
to
provide
an
impressive
diversity
reaction
pathways,
such
1,3‐dipolar
cycloadditions,
various
types
cyclizations,
along
with
a
wide
variety
more
complex
domino/tandem
reactions,
allowing
many
novel
heterocyclic
products
be
achieved
high
enantioselectivities.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(44), P. 8005 - 8009
Published: Oct. 31, 2023
A
catalytic
asymmetric
tandem
cyclization
of
azadienes
and
ortho-alkynylnaphthols
accelerated
by
the
chiral
N,N′-dioxide-gadolinium(III)
complex
is
disclosed.
This
method
allows
synthesis
a
range
1,2-dihydrobenzofuro[3,2-b]pyridines
containing
both
axially
centrally
elements
in
high
yields
excellent
stereoselectivities
(up
to
>99%
yield,
91:9
dr,
98%
ee).
control
experiment
revealed
that
this
process
proceeded
through
multistep
[2
+
2]
cycloaddition/retroelectrocyclization/tautomerism/1,6-conjugate
addition
cascade.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(33), P. 13299 - 13305
Published: Jan. 1, 2024
An
asymmetric
tandem
allylic
C–H
amination
and
[2,3]-sigmatropic
rearrangement
has
been
developed
by
making
use
of
bimetallic
relay
catalysis
with
an
achiral
Pd(0)
catalyst
a
chiral
N,N
′-dioxide-Mg(
ii
)
complex.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3844 - 3849
Published: April 25, 2024
The
catalytic
asymmetric
[3
+
2]
cycloaddition
of
racemic
norcaradienes
with
quinones
to
construct
multicyclic
hydrodibenzofurans
was
achieved
by
the
use
chiral
N,N′-dioxide/metal
complex
catalysts.
Kinetic
resolution
accompanied
partial
racemization
occurred,
and
one
enantiomer
in
prior
acted
as
C2
synthon
participate
diastereoselective
cycloaddition.
An
enantiodivergent
synthesis
via
a
switch
metal
ions
observed
when
naphthoquinone
used
partner.
DFT
calculations
revealed
profiles
processes.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 14, 2025
A
highly
diastereo-
and
enantioselective
dearomative
Diels-Alder
reaction
was
accomplished
by
chiral
N,N'-dioxide/Mg(II)
complex
catalyst.
Various
anthracene
derivatives
methyleneindolinones
efficiently
transformed
into
the
corresponding
spiro-bridged
cyclic
products
with
four
consecutive
stereocenters
in
good
yields,
excellent
dr
er
values
under
mild
conditions
(46
examples,
up
to
99%
yield,
>19:1
dr,
>99:1
er).
Gram-scale
synthesis
of
their
further
transformations
were
feasible.
On
basis
theoretical
calculation,
possible
working
modes
provided
understand
origin
stereoselectivity
this
transformation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 19, 2024
Abstract
The
design
of
various
cycloaddition/annulation
processes
is
one
the
most
intriguing
challenges
in
development
donor‐acceptor
(D–A)
cyclopropane
chemistry.
In
this
work,
a
new
class
formal
high‐order
[6+n]‐cycloaddition
and
annulation
D–A
cyclopropanes
with
cycloheptatriene
systems
has
been
designed
reported,
to
fill
significant
gap
chemistry
cyclopropanes.
reactivity
methylated
cycloheptatrienes
from
Me1
Me5
as
well
unsubstituted
was
studied
detail
under
GaCl
3
activation
conditions,
which
makes
it
possible
efficiently
generate
gallium
1,2‐zwitterionic
complexes
or
1,3‐zwitterionic
intermediates
starting
cyclopropanes,
while
other
Lewis
acids
are
ineffective
non‐selective.
New
examples
[6+2]‐,
[6+3]‐,
[6+4]‐,
[6+1]‐,
[4+2]‐cycloaddition
reactions
along
more
complex
were
discovered.
Cycloheptatriene
itself
can
also
successfully
act
hydride
anion
donor,
allows
ionic
hydrogenation
be
performed
mild
conditions.
As
result,
number
efficient
highly
diastereoselective
protocols
for
synthesis
seven‐membered
carbocycles
developed.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(58), P. 7507 - 7510
Published: Jan. 1, 2024
An
asymmetric
dearomatization
reaction
of
benzyl
1-naphthyl
ethers
accelerated
by
a
chiral
N
,
′-dioxide/Co(
ii
)
complex
is
disclosed.
Experiment
results
indicated
that
the
proceeds
via
tight
ion-pair
intermediate.
