The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(5), С. 2508 - 2519
Опубликована: Фев. 18, 2022
Bowl-shaped
aromatic
molecules,
buckybowls,
are
attractive
molecules
because
of
the
unique
properties
derived
from
their
curved-π
scaffolds.
Doping
heteroatoms
into
buckybowl
frameworks
is
a
powerful
method
to
change
structural
and
electronical
properties.
Herein,
we
report
synthesis
C70
fragment
buckybowl,
homosumanene,
heterahomosumanenes
having
lactone
moiety
lactam
via
three
ring-expansion
reactions
using
sumanenone
as
common
intermediate.
X-ray
diffraction
analysis
single
crystals
reveals
columnar
packing
structure
with
shallow
bowl-depth.
The
readily
derivatized
give
azahomosumanene
derivatives,
nitrogen-doped
analogues
homosumanene
possessing
pyridine
ring
at
peripheral
carbon.
synthetic
application
α-phenyl
cyclometalating
ligand
platinum
also
revealed
its
utility
for
preparing
metal
complex
bearing
ligand.
Green Chemistry,
Год журнала:
2024,
Номер
26(7), С. 3786 - 3790
Опубликована: Янв. 1, 2024
A
hitherto
unreported
catalyst-free
ring
expansion
reaction
of
tetrahydroisoquinolines
with
o
-alkynylarylaldehydes
for
the
construction
dibenzo[
b
,
d
]azepine
skeleton
is
described.
Chemical Communications,
Год журнала:
2024,
Номер
60(38), С. 4999 - 5009
Опубликована: Янв. 1, 2024
This
Feature
Article
discusses
recent
advances
in
the
development
of
cascade
ring
expansion
reactions
for
synthesis
medium-sized
rings
and
macrocycles.
Cascade
have
much
potential
use
biologically
important
macrocycles,
most
notably
as
they
don't
require
high
dilution
conditions,
which
are
commonly
used
established
end-to-end
macrocyclisation
methods.
Operation
by
method
can
allow
large
products
to
be
accessed
European Journal of Organic Chemistry,
Год журнала:
2021,
Номер
2021(48), С. 6781 - 6805
Опубликована: Окт. 30, 2021
Abstract
Due
to
the
high
reactivity
of
cyclopropanes,
different
methods
have
been
developed
for
their
stereo‐
and
regio‐controlled
ring‐opening
reactions
achieve
a
variety
synthetically
useful
targets.
The
traditional
include
thermolysis,
use
oxidants,
transition
metals
or
radical
precursors
in
which
many
them
encounter
various
difficulties.
In
past
several
years,
visible‐light‐mediated
photoredox
received
considerable
attention
organic
transformations.
Several
methodologies
recent
times
cyclopropanes.
Considering
synthetic
potential
this
class
reactions,
we
provide
summary
cyclopropane
under
visible‐light
catalysis.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(46), С. 21363 - 21370
Опубликована: Ноя. 9, 2022
The
stepwise
reduction
of
a
doubly
cyclic
alkyl(amino)carbene
(CAAC)-stabilized
2,3-bis(dibromoboryl)naphthalene
enables
the
isolation
corresponding
mono-
and
bis(boryl)
radicals
(one-
two-electron
reduction),
2π-aromatic
1,2-diborete
(four-electron
which
shows
biradical
character
in
solid-state
EPR
spectrum,
its
bis(alkylidene)diboron
dianion
(six-electron
reduction).
X-ray
crystallographic
analysis
diborete
highly
strained
twisted
four-membered
ring
with
formal
cis-diborene
motif
featuring
very
elongated
B-B
double
bond.
Calculations
based
on
DFT
multireference
approaches
reveal
that
possesses
an
open-shell
singlet
biradicaloid
ground
state,
is
slightly
energetically
preferred
to
EPR-active
triplet-state
congener.
addition
CO
resulted
bond
splitting
formation
closed-shell
singlet,
Lewis
base-stabilized
bis(borylene),
whereas
twofold
γ
insertion
phenyl
azide
generates
1,3-bis(diazenyl)-1,3,2,4-diazadiboretidine.
Organic Letters,
Год журнала:
2024,
Номер
26(9), С. 1819 - 1823
Опубликована: Фев. 28, 2024
Ring
expansion
of
strained
small
rings
provides
an
efficient
method
for
the
synthesis
various
high-value
carbocycles
and
heterocycles.
Here
we
report
BF3·Et2O
as
both
activating
reagent
fluorine
source,
enabling
ring
phosphirane
P–F
bond
formation.
Treatment
1-iminylphosphirane
complexes
with
resulted
in
1,2-azaphospholidines,
while
reaction
1-acylphosphirane
afforded
1,2-dihydrophosphetes.
The
path
was
tuned
by
nucleophilicity
N
O
atoms
toward
intermediate
phosphenium
cation.
Precise
skeletal
manipulation
involving
insertion,
deletion,
and
replacement
has
garnered
considerable
attention
within
the
synthetic
chemistry
community.
Among
these
processes,
multi-atom
insertion
reactions
in
acyclic
compounds
remain
a
formidable
challenge,
primarily
due
to
low
efficiency
of
fragment
recapture
after
cleavage,
which
results
from
lack
substrate-specific
proximity
during
reconstruction
stage.
Here,
we
report
an
asymmetric
reaction
esters
via
Rh-catalyzed
ring
opening
oxabicyclic
alkenes,
achieving
excellent
regio-,
diastereo-,
enantioselectivity.
This
approach
enables
efficient
rapid
construction
molecular
library
with
chiral
hydroxy-dihydronaphthalene
scaffold,
showcasing
atom-efficient
reaction.
Detailed
density
functional
theory
calculations
reveal
key
mechanistic
features
stereoselectivity-determining
model
this
transformation.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 14, 2025
Skeletal
manipulation
of
aromatic
compounds
has
emerged
as
a
potent
tool
in
synthetic
chemistry,
but
simultaneous
multiring
remains
largely
unexplored
due
to
the
inherent
complexities
ring
and
site
selectivity.
Herein,
we
report
an
unprecedented
skeletal
that
fuses
four
5-membered
rings,
comprising
two
organic
metal-containing
systems,
into
novel
metal-bridged
6/6/6/6-membered
scaffold.
The
sequential
fusion
is
accomplished
through
atom-mutual-embedding
strategy;
this
strategy
entails
stepwise
insertion
nitrogen
atoms
separate
metal-carbon
bonds
simultaneously
integrates
metal
atom
bridge
across
isoxazole
moieties.
presence
central
crucial
for
ensuring
precise
substrate
alignment
enhancing
both
specificity.
resulting
tetrahexacyclic
products
exhibit
remarkable
stability
superior
near-infrared
(NIR)
functional
properties,
surpassing
those
precursor
compounds.
This
work
not
only
establishes
conceptual
foundation
designing
versatile
molecules
amenable
intricate
editing
also
contributes
rational
performance-targeted
molecular
architectures.
Organic Letters,
Год журнала:
2022,
Номер
24(40), С. 7323 - 7327
Опубликована: Окт. 3, 2022
Herein,
we
report
the
metal-free
synthesis
of
imidized
methylene
cyclobutane
derivatives
via
a
strain-release
driven
addition
reaction
[1.1.1]propellane.
Using
this
strategy,
cyclobutyl
cation
intermediate
generated
by
protonation
[1.1.1]propellane
was
found
to
be
trapped
nitriles
form
nitrilium
ion
intermediate,
which
subsequently
reacted
with
carboxylic
acids
produce
cyclobutene
Mumm-type
rearrangement.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(7)
Опубликована: Ноя. 23, 2022
Methylenecyclobutanes
are
found
to
undergo
Wacker
oxidation
via
a
semi-pinacol-type
rearrangement.
Key
successful
process
is
the
use
of
tert-butyl
nitrite
as
oxidant,
which
not
only
enables
efficient
catalyst
turn-over
but
also
ensures
high
Markovnikov-selectivity
under
mild
conditions.
Thus,
cyclopentanones
(26
examples)
can
be
accessed
in
an
overall
good
yield
and
excellent
selectivity
(up
97
%
yield,
generally
>99
:
1
ketone:aldehyde
ratio).
Stereochemical
analysis
reaction
sequence
reveals
migration
aptitudes
line
with
related
1,2-shifts.
By
introducing
pyox
ligand
palladium,
prochiral
methylenecyclobutanes
desymmetrized,
thus
realizing
first
enantioselective
oxidation.
