Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(20)
Published: Sept. 11, 2023
An
efficient
and
convenient
strategy
for
Ir-catalyzed
selective
B(3)-amination
of
o-carboranes
with
amines
via
acceptorless
BH/NH
dehydrocoupling
was
developed,
affording
a
series
B(3)-aminated-o-carboranes
in
moderate
to
high
isolated
yields
H2
gas
as
sole
by-product.
Such
an
oxidant-free
system
endues
the
protocol
sustainability,
atom-economy
environmental
friendliness.
A
reaction
mechanism
Ir(I)-Ir(III)-Ir(I)
catalytic
cycle
involving
oxidative
addition,
dehydrogenation
reductive
elimination
proposed.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 3, 2025
Selective
functionalization
of
o-carboranes
has
received
tremendous
attention,
specifically
in
the
regioselective
modification
ten
chemically
similar
BH
vertices
within
o-carborane
cage.
We
disclose
herein
a
strategy
for
palladium-catalyzed
esterification
B(3)-H
bond
using
tungsten
hexacarbonyl
as
carbon
monoxide
source.
The
corresponding
functionalized
were
prepared
moderate
to
very
good
yields
with
excellent
regioselectivity.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
Transition
metal
catalyzed
selective
cage
B–H
functionalization
of
carboranes
has
made
significant
progress
in
recent
years,
giving
rise
to
the
efficient
synthesis
a
large
variety
B-functionalized
including
alkenylation,
arylation,
alkynylation,
borylation,
hydroxylation,
acyloxylation,
amination,
and
halogenation.
However,
mechanisms
these
catalytic
B–X
coupling
reactions
are
not
well
understood.
Herein,
we
describe
isolation
characterization
catalytically
relevant
o-carborane
based
palladium(II)
metallacycle,
disclosing
details
Pd-catalyzed
o-carboranes.
As
result,
highly
B(3,6)-dihalogenation,
-dimethylation,
-diarylation
o-carboranes
have
been
achieved.
Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 11, 2024
Abstract
Carboranes
are
a
type
of
molecular
clusters
consisting
carbon,
hydrogen,
and
boron
atoms.
They
possess
unique
characteristics,
such
as
three-dimensional
aromaticity,
icosahedral
geometry,
robustness.
Functionalized
carboranes
have
been
utilized
in
various
fields,
including
medicine,
materials,
organometallic/coordination
chemistry.
In
this
context,
selective
functionalization
o-carboranes
has
received
tremendous
attention,
specifically
the
regio-
enantioselective
modification
ten
chemically
similar
BH
vertices
within
carborane
cage.
recent
years,
significant
progress
made
catalytic
vertex-specific
functionalization,
well
achieving
cage
BH.
This
review
provides
an
overview
advancements
research
field.
1
Introduction
2
Carboxy-Assisted
Functionalization
2.1
Formation
B–C
Bonds
2.2
B–N
2.3
B–O
2.4
B–X
2.5
Consecutive
B–Y
(Y
=
N,
O)
3
N-Based
Directing-Group-Assisted
B–H
3.1
Acylamino
Directing
Group
3.2
Amide
3.3
Pyridyl
3.4
Imine
4
Phosphinyl-Assisted
Cage
5
Bidentate-Directing-Group-Assisted
6
Other
7
Conclusions
Inorganic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
nickel-catalyzed
direct
cage
B–H
poly-chalcogenation
of
icosahedral
carborane
clusters,
enabled
by
a
variable
bidentate
8-aminoquinoline
traceless
directing
group,
has
been
developed
under
oxidant-free
and
weakly
basic
conditions.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(2), P. 129 - 134
Published: Sept. 19, 2023
Comprehensive
Summary
This
work
describes
a
general
method
for
the
synthesis
of
series
sulfenylated
and
selenylated
carboranes
at
room
temperature
using
readily
available
iodocarboranes
as
starting
materials
via
boron‐centered
carboranyl
radicals.
Such
hypervalent
boron
radicals
are
generated
by
visible‐light‐promoted
Pd(0)/Pd(I)
pathway.
They
useful
intermediates
can
be
trapped
disulfides
phenylselenyl
chloride
convenient
construction
B—S/Se
bonds.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(12), P. 5481 - 5486
Published: March 6, 2024
The
discovery
of
ferrocene
in
1951
was
a
significant
landmark
the
field
organometallic
chemistry,
and
since
then,
numerous
sandwich-
or
half-sandwich
metallic
complexes
have
been
reported.
However,
silver
stands
as
an
intriguing
exception
this
regard,
knowledge
its
bonding
situation
has
remained
undisclosed.
Herein,
unprecedented
12-vertex
metallacarboranes
Ag(I)
(2a
2b)
were
synthesized
through
reaction
sodium
hexamethyldisilazide
(NaHMDS)
with
mixture
nido-C2B9
carborane
anion-supported
N-heterocyclic
carbene
precursors
(1a
1b)
[Ag(PPh3)Cl]4.
X-ray
structural
analysis
resulting
revealed
unique
"slipped"
structure,
which
is
rarity
among
cyclopentadienyl
analogues.
DFT
calculations
provided
insights
into
asymmetric
π-interactions
between
pentagonal
C2B3
face
ion.
