Chelating 1,2-Bis(2′-picolyl)-o-carborane as a Supporting Ligand for Pd-Catalyzed Selective B(3,6)–H Difunctionalization of o-Carboranes
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 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.
Язык: Английский
Palladium-Catalyzed Regioselective B(3,4,5,6)–H Tetra-Arylation of o-Carboranes
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 21, 2025
A
transition-metal-catalyzed
iterative
multiple
cage
B-H
activation
reaction
for
constructing
multifunctionalization
of
o-carboranes
in
one
pot
is
challenging.
Herein,
palladium-catalyzed
regioselective
tetra-arylation
a
wide
range
C(1)-N-aryl-o-carboranyl
amides
with
aryl
iodides
has
been
developed.
variety
B(3,4,5,6)-tetra-arylated
were
synthesized
good-to-excellent
yields.
Moreover,
the
mono-,
di-,
and
triarylated
intermediate
products
isolated,
exact
structures
determined
by
NMR,
high-resolution
mass
spectrometry,
X-ray
analysis,
which
provide
rationale
that
order
introduction
groups
into
o-carborane
B(4)
>
B(5)
B(3)/B(6).
This
protocol
represents
powerful
synthetic
method
polyfunctionalization
derivatives
under
very
mild
simple
conditions,
offers
valuable
reference
design
synthesis
molecular
propellers
based
on
carboranes.
Язык: Английский
Directing Group Assisted Transition Metal Catalyzed Selective BH Functionalization of o-Carboranes
Synthesis,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 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
Язык: Английский