Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 15, 2024
Abstract
Carborane
compounds,
known
for
their
exceptional
thermal
stability
and
non‐toxic
attributes,
have
garnered
widespread
utility
in
medicine,
supramolecular
design,
coordination/organometallic
chemistry,
others.
Although
there
is
considerable
interest
among
chemists,
the
integration
of
suitable
carborane
molecules
into
ferroelectric
materials
remains
a
formidable
challenge.
In
this
study,
we
employ
quasi‐spherical
design
strategy
to
introduce
functional
groups
at
boron
vertices
o
‐carborane
cage,
aiming
reduce
molecular
symmetry.
This
approach
led
successful
synthesis
pioneering
crystals
composed
cage‐like
carboranes:
9‐OH‐
(
1
)
9‐SH‐
2
),
which
undergo
above‐room
phase
transitions
T
c
approximately
367
K
347
K.
Interestingly,
represent
uniaxial
multiaxial
ferroelectrics
respectively,
with
exhibiting
six
polar
axes
as
many
twelve
equivalent
polarization
directions.
As
instance
crystals,
study
introduces
novel
structural
archetype
ferroelectrics,
thereby
providing
fresh
insights
exploration
promising
applications.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 14, 2025
Carboranyl
amines
are
distinct
from
typical
organic
amines.
Due
to
the
electronic
influence
of
carborane
cage,
they
have
low
nucleophilicity
and
reluctant
alkylate.
Moreover,
asymmetric
synthesis
chiral
carboranes
is
still
in
its
infancy.
Herein
we
achieved
first
catalytic
N-alkylation
o-carboranyl
amine,
providing
general
access
diverse
secondary
with
high
efficiency
enantioselectivity
under
mild
conditions.
For
time,
organocatalysis
was
introduced
chemistry.
Key
success
use
situ
generated
(naphtho-)quinone
methides
as
alkylating
reagents
suitable
acid
catalysts.
This
protocol
also
applicable
S-alkylation
1-SH-o-C2B10H11.
Control
experiments
kinetic
studies
provided
important
insights
into
reaction
mechanism,
which
likely
involves
rate-determining
generation
quinone
methide
followed
by
fast
enantio-determining
nucleophilic
addition.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 15, 2024
Carborane
compounds,
known
for
their
exceptional
thermal
stability
and
non-toxic
attributes,
have
garnered
widespread
utility
in
medicine,
supramolecular
design,
coordination/organometallic
chemistry,
others.
Although
there
is
considerable
interest
among
chemists,
the
integration
of
suitable
carborane
molecules
into
ferroelectric
materials
remains
a
formidable
challenge.
In
this
study,
we
employ
quasi-spherical
design
strategy
to
introduce
functional
groups
at
boron
vertices
o-carborane
cage,
aiming
reduce
molecular
symmetry.
This
approach
led
successful
synthesis
pioneering
crystals
composed
cage-like
carboranes:
9-OH-o-carborane
(1)
9-SH-o-carborane
(2),
which
undergo
above-room
phase
transitions
(T
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(12), С. 3074 - 3079
Опубликована: Янв. 1, 2023
This
frontier
article
summarizes
the
recent
developments
in
base
metal-catalyzed
regioselective
cage
B–H
functionalization
of
carboranes
and
discusses
related
challenging
issues.
Organometallics,
Год журнала:
2024,
Номер
43(10), С. 1077 - 1084
Опубликована: Май 16, 2024
Nucleophilic
substitution
of
B–H
is
an
important
strategy
for
the
synthesis
carborane
derivatives.
Although
intermolecular
nucleophilic
has
been
widely
explored,
intramolecular
rarely
reported.
Herein,
we
synthesized
a
novel
carborane-fused
N-heteroaromatic
through
transition-metal-free
reaction
between
carboranyl
lithium
and
2,3-dichloroquinoxaline.
Two
C–Cl
substitutions
one
with
were
involved
in
this
transformation.
Instead
most
electron-deficient
B(3)–H
vertex,
selectively
occurred
on
B(4)–H
vertex.
This
method
provides
new
ring
compounds.
Organic Letters,
Год журнала:
2022,
Номер
24(39), С. 7077 - 7081
Опубликована: Сен. 23, 2022
We
report
here
a
catalytic
selective
cage
B4-H
amination
of
o-carboranes
employing
an
Ir(III)
complex
as
catalyst
and
anthranils
aminating
agents,
leading
to
large
class
B4-aminated
with
very
high
yields
broad
substrate
scope
under
mild
conditions
without
any
oxidants.
In
these
reactions,
the
carboxyl
group
serves
traceless
directing
unit
determine
site
selectivity
degree
substitution.
Chemical Communications,
Год журнала:
2022,
Номер
58(60), С. 8392 - 8395
Опубликована: Янв. 1, 2022
A
unique
approach
to
vertex-selective
catalytic
B-H
amination
at
either
the
B(3)-
or
B(4)-position
in
o-carboranes
has
been
developed.
Using
different
transition
metal
catalysts,
dehydrogenative
BH/NH
cross-coupling
of
and
free
amines
achieved,
leading
a
wide
variety
cage
B(4)-aminated
moderate
high
yields
with
excellent
regioselectivity,
where
carboranyl
carboxylic
acids
can
serve
as
competent
coupling
partners
without
any
pre-functionalization.
The
isolation
structural
identification
key
intermediate
provide
an
insight
into
reaction
mechanism
B(4)-H
amination.
Chemical Science,
Год журнала:
2024,
Номер
15(27), С. 10392 - 10401
Опубликована: Янв. 1, 2024
A
Pd-catalyzed
cross-coupling
system
has
been
developed
to
achieve
vicinal
diamination
of
9,10-dibromo-carborane
with
NH-heterocycles
and
anilines.
These
products
can
be
further
converted
carborane-fused
six-
seven-membered
heterocycles.
Organic Letters,
Год журнала:
2023,
Номер
25(32), С. 5989 - 5994
Опубликована: Авг. 4, 2023
Iridium(III)-catalyzed
regioselective
B(4)-H
amination
is
developed
from
the
reaction
of
o-carborane
acids
with
sulfilimines
without
any
oxidants
under
mild
conditions,
which
leads
to
a
wide
range
aminated
o-carboranes
in
good
yields
broad
substrate
scope.
Moreover,
selective
B(3,6)-diamination
acid
was
achieved.
The
present
attractive
practical
point
view
because
dibenzothiophene
quantitatively
recovered
and
reused.
Chinese Journal of Chemistry,
Год журнала:
2022,
Номер
41(3), С. 307 - 313
Опубликована: Окт. 22, 2022
Comprehensive
Summary
Herein,
we
describe
the
synthesis
of
a
carborane‐supported
octanuclear
palladacycle
complex,
Pd
8
(
o
‐C
2
B
10
H
CS
CH
3
)
4
Cl
(CH
CN)
(complex
1
),
with
B(3)–H
activations
on
‐carborane
ligand.
The
substitution
reaction
has
been
explored,
and
three
its
substituted
complexes
(L)
(L
=
t
BuNC,
;
L
C
5
N,
S,
have
synthesized.
m
‐
p
disubstituted
ligands
(CS
(ligands
6
as
well
their
B—H
activated
carborane
[
9
PdCl]
7
][PdCl(
BuNC)]
also
synthesized
by
similar
method.
All
these
characterized,
including
X‐ray
single
crystal
diffraction,
NMR
spectroscopy,
IR
spectroscopy
elemental
analysis
methods.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
12(3)
Опубликована: Дек. 21, 2022
Abstract
A
ruthenium‐catalyzed
selective
B4
amidation
of
o
‐carboranes
with
a
variety
alkyl‐,
aryl‐,
and
heteroaryl‐substituted
dioxazolones
is
developed
by
carboxylic
acid‐assisted
B(4)‐H
bond
activation
in
‐carborane
acids,
affording
multitude
(4)‐amidated
good
yields
the
evolution
carbon
dioxide.
In
addition,
two‐fold
decarboxylative
reaction
cage
was
accomplished.
