Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(13), С. 4508 - 4511
Опубликована: Март 26, 2018
Carborane
cage
chirality
is
an
outstanding
issue
of
great
interest
as
the
icosahedral
carboranes
have
wide
applications
in
medicinal
and
materials
chemistry.
The
synthesis
optically
active
carborane
derivatives,
whose
associated
with
substitution
patterns
on
polyhedron,
will
open
new
avenues
to
We
report
herein
efficient
method
achieve
chiral-at-cage
arylation
o-carboranes
high
regio-
enantioselectivities
by
a
strategy
palladium-catalyzed
asymmetric
intramolecular
B-H
cyclization.
This
represents
first
example
enantioselective
reaction
carboranes,
providing
way
for
construction
compounds
skeletons.
Chemical Reviews,
Год журнала:
2022,
Номер
122(15), С. 12544 - 12747
Опубликована: Июль 17, 2022
1,1,1,3,3,3-Hexafluoroisopropanol
(HFIP)
is
a
polar,
strongly
hydrogen
bond-donating
solvent
that
has
found
numerous
uses
in
organic
synthesis
due
to
its
ability
stabilize
ionic
species,
transfer
protons,
and
engage
range
of
other
intermolecular
interactions.
The
use
this
exponentially
increased
the
past
decade
become
choice
some
areas,
such
as
C–H
functionalization
chemistry.
In
review,
following
brief
history
HFIP
an
overview
physical
properties,
literature
examples
reactions
using
or
additive
are
presented,
emphasizing
effect
each
reaction.
Chemical Society Reviews,
Год журнала:
2019,
Номер
48(13), С. 3660 - 3673
Опубликована: Янв. 1, 2019
This
review
summarizes
recent
advances
in
transition
metal
catalyzed
vertex-specific
BH
functionalization
ofo-carborane
for
controlled
synthesis
of
its
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(10), С. 3162 - 3166
Опубликована: Янв. 30, 2019
Abstract
The
aggregation‐induced
electrochemiluminescence
(AIECL)
of
carboranyl
carbazoles
in
aqueous
media
was
investigated
for
the
first
time.
Quantum
yields,
morphologies,
and
particle
sizes
were
observed
to
determine
(ECL)
performance
these
aggregated
organic
dots
(ODs).
All
compounds
exhibit
much
higher
ECL
stability
intensity
than
carborane‐free
compound,
demonstrating
essential
role
motif.
Moreover,
results
cyclic
voltammetry
(CV)
suggest
that
oxidation/reduction
reactions
take
place
at
excited
states
ODs
proposed
be
generated
by
mechanism
surface
state
transitions.
More
importantly,
show
a
reductive–oxidative
contrast
other
materials
oxidative–reductive
mechanisms.
Our
experiments
data
have
established
relation
between
AIE
structures
properties
has
strong
potential
biological
diagnostic
applications.
Accounts of Chemical Research,
Год журнала:
2021,
Номер
54(21), С. 4065 - 4079
Опубликована: Окт. 24, 2021
ConspectusCarboranes
are
a
class
of
polyhedral
carbon-boron
molecular
clusters
featuring
three-dimensional
aromaticity,
which
often
considered
as
3D
analogues
benzene.
Their
unique
structural
and
electronic
properties
make
them
invaluable
building
blocks
for
applications
ranging
from
functional
materials
to
versatile
ligands
pharmaceuticals.
Thus,
selective
functionalization
carboranes
has
received
tremendous
research
interest.
In
earlier
days,
the
vast
majority
works
in
this
area
were
focused
on
cage
carbon
via
facile
deprotonation
CH,
followed
by
reaction
with
electrophiles.
On
contrary,
B-H
activation
is
very
challenging
since
10
bonds
o-carborane
similar,
how
achieve
desired
transformation
at
specific
boron
vertex
long-standing
issue.As
more
electronegative
than
boron,
property
results
different
charges
cage,
follow
order
B(3,6)-H
≪
B(4,5,7,11)-H
<
B(8,10)-H
B(9,12)-H.
We
thought
that
difference
may
trigger
favorite
interaction
proper
transition
metal
complex
bond
carborane,
could
be
utilized
solve
selectivity
issue.
Accordingly,
our
strategy
described
follows:
(1)
electron-rich
catalysts
good
most
electron-deficient
(connected
both
C-H
vertices);
(2)
relatively
B(8,9,10,12)-H
(with
no
bonding
either
(3)
directing-group-assisted
catalysis
appropriate
only
one
vertex),
whose
lie
middle
range
bonds.
This
been
successfully
applied
laboratory
other
groups
development
series
synthetic
routes
catalytic
carborane
resulting
synthesis
large
number
cage-boron-functionalized
derivatives
regioselective
fashion.
Subsequently,
significant
progress
emerging
made.In
2013
we
reported
tetrafluorination
o-carboranes
using
an
Pd(II)
salt,
[Pd(MeCN)4][BF4],
catalyst.
2014
disclosed
first
example
carboxy-directed
alkenylation
B(4)
promoted
Ir(III)
2017
presented
Ir(I)-catalyzed
diborylation
also
uncovered
Pd-catalyzed
asymmetric
chiral-at-cage
2018.
These
proof-of-principle
studies
have
greatly
stimulated
activities
enabled
catalysts.
so
far
developed
toolbox
methods
B-olefination,
-arylation,
-alkenylation,
-alkynylation,
-oxygenation,
-sulfenylation,
-borylation,
-halogenation,
-amination.
recently
expanded
base
catalysis.
As
field
progresses,
expect
will
invented,
detailed
Account
promote
these
efforts.
Organic & Biomolecular Chemistry,
Год журнала:
2018,
Номер
16(25), С. 4582 - 4595
Опубликована: Янв. 1, 2018
C-H
functionalisation
promises
a
paradigm
shift
in
synthetic
planning.
However,
the
additional
steps
often
required
to
install
and
remove
directing
groups
currently
detract
from
efficiency.
The
strategy
of
reversible
installation
group
via
an
imine
linkage
has
recently
emerged,
with
formed
hydrolysed
situ.
Such
transient
can
promote
transition
metal
catalysed
unactivated
bonds
aldehydes,
ketones
amines.
This
approach
removes
usually
for
covalent
use
catalytic
quantities
forming
component.
review
updates
rapidly
developing
field
on
sp2
sp3
carbon
centres,
form
new
C-C
C-X
bonds.
We
focus
structures
as
mono
or
bidentate
coordinating
various
catalysts.
Chemistry - A European Journal,
Год журнала:
2017,
Номер
24(12), С. 2795 - 2805
Опубликована: Ноя. 17, 2017
Abstract
Carboranes
are
a
class
of
carbon–boron
molecular
clusters
with
unusual
thermal
and
chemical
stabilities.
They
have
been
proved
as
very
useful
building
blocks
in
supramolecular
design,
optoelectronics,
nanomaterials,
boron
neutron
capture
therapy
agents
organometallic/coordination
chemistry.
Thus,
the
functionalization
o
‐carboranes
has
received
growing
interests.
Over
past
decades,
most
works
this
area
focused
on
cage
carbon
weakly
acidic
C−H
proton
can
be
readily
deprotonated
by
strong
bases.
In
sharp
contrast,
selective
B−H
activation/functionalization
among
chemically
similar
ten
vertices
is
challenging.
Considering
differences
electron
density
bonds
‐carborane
nature
transition
metal
complexes,
we
tackled
selectivity
issue
means
organometallic
Our
strategy
follows:
using
electron‐rich
catalysts
for
electron‐deficient
B(3,6)−H
(bonded
to
both
CH
vertices);
transition‐metal
relatively
B(8,9,10,12)−H
(with
no
bonding
combination
directing
groups
electrophilic
B(4,5,7,11)−H
only
one
vertex).
Successful
applications
such
result
preparation
large
variety
B‐functionalized
carboranes
regioselective
catalytic
manner,
which
inaccessible
other
means.
It
believed
that
field
progresses,
expected
synthesized,
results
detailed
concept
article
will
further
these
efforts.
Chemical Communications,
Год журнала:
2017,
Номер
54(6), С. 689 - 692
Опубликована: Дек. 21, 2017
Palladium-catalyzed
enantioselective
C(sp2)-H
activation
of
ferrocenyl
ketones
is
achieved
through
utilizing
catalytic,
inexpensive
l-tert-leucine
as
a
chiral
transient
directing
group.
The
transformation
allows
rapid
access
to
ferrocene
scaffolds
simultaneously
possessing
planar-
and
stereogenic
central
chirality,
widely
applied
in
the
ferrocene-based
ligand
families.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
57(13), С. 3401 - 3405
Опубликована: Янв. 30, 2018
Abstract
Reported
herein
is
the
first
example
of
a
direct
arylation
heteroarenes
by
transient‐ligand‐directed
strategy
without
need
to
construct
and
deconstruct
directing
group.
A
wide
range
undergoes
coupling
with
diverse
aryl
iodides
assemble
large
library
highly
selective
functionalized
3‐arylthiophene‐2‐carbaldehydes.
This
route
provides
an
opportunity
rapidly
access
new
mechanofluorochromic
materials.
Moreover,
novel
for
mechanochromic
luminogens
chromism
trends
red‐
blue‐shifts
has
been
disclosed
time
facile
functional‐group
modifications
common
structural
core.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(42), С. 13798 - 13807
Опубликована: Сен. 19, 2018
A
series
of
cage
penta-arylated
carboranes
have
been
synthesized
by
palladium-catalyzed
intermolecular
coupling
the
C-carboxylic
acid
monocarba-
closo-dodecaborate
anion
[CB11H12]-
with
iodoarenes
direct
B-H
bond
functionalization.
These
transformations
set
a
record
in
terms
one-pot
directing
group-mediated
activation
inert
bonds
single
molecule.
The
methodology
is
characterized
high
yields,
good
functional
group
tolerance,
and
complete
regioselectivity.
COOH
can
be
easily
removed
during
or
after
reaction.
mechanistic
pathways
were
probed
using
density
theory
calculations.
Pd(II)-Pd(IV)-Pd(II)
catalytic
cycle
proposed,
which
initial
followed
preferred
adjacent
boron
vertex,
continuation
this
selectivity
results
continuous
walking
process
palladium
center.
opens
new
avenue
toward
building
blocks
5-fold
symmetry.