Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 3, 2024
Abstract
Fluorinated
arenes
play
a
crucial
role
in
drug
discovery,
specialty
materials,
and
medical
imaging.
Although
several
variants
for
Cu‐mediated
nucleophilic
fluorination
of
arylboronic
acids
derivatives
have
been
developed,
these
protocols
rarely
address
the
occurrence
control
protodeboronation,
which
greatly
complicates
product
separation
can
compromise
effectiveness
radiotracer
vivo
Consequently,
simpler
more
efficient
procedures
are
needed
to
allow
rapid
18
F/
19
F‐fluorination
both
esters
while
minimizing
protodeboronation.
Mechanistic
controls
revealed
that
addition
high
temperature,
strong
donor
ligands
such
as
acetonitrile
pyridine
accentuate
This
observation
guided
optimization
ligandless
procedure,
with
t
‐BuOH
solvent,
activate
fluoride
under
milder
conditions
at
lower
temperatures
Additionally,
new
copper
salt,
Cu(ONf)
2
was
employed
further
improve
efficiency.
A
large
range
functional
groups
tolerated
is
complete
within
30
minutes
temperature
60
°C,
affords
fluorinated
heteroarenes
39
%
84
yield.
With
minimal
modifications,
protocol
also
be
applied
F‐radiofluorination,
affording
radiochemical
conversions
(RCCs)
between
17
54
protodeboronation
compared
previously
established
protocols.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 7, 2023
In
this
article
we
report
that
a
cationic
version
of
Akiba's
BiIII
complex
catalyzes
the
reduction
amides
to
amines
using
silane
as
hydride
donor.
The
catalytic
system
features
low
catalyst
loadings
and
mild
conditions,
en
route
secondary
tertiary
aryl-
alkylamines.
tolerates
functional
groups
such
alkene,
ester,
nitrile,
furan
thiophene.
Kinetic
studies
on
reaction
mechanism
result
in
identification
network
with
an
important
product
inhibition
is
agreement
experimental
profiles.
Dalton Transactions,
Год журнала:
2023,
Номер
52(36), С. 12597 - 12603
Опубликована: Янв. 1, 2023
Hypervalent
(three-center,
four-electron)
bonding
in
organobismuth
complexes
has
demonstrated
to
activate
bonds
and
perturb
electron
configurations
promoting
synthesis,
catalysis,
materials,
other
applications.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12372 - 12384
Опубликована: Авг. 5, 2024
The
controllable
selective
oxidation
of
anilines
to
metastable
and
valuable
products
mediated
by
a
single
catalyst
represents
long-standing
synthetic
challenge
due
the
numerous
active
species
generated
in
situ
their
intricate
interactions.
This
study
introduces
synthesis
μ-oxo-bridged
dinuclear
tungsten
complex
[W(O)2(Cl)4-MeObpy]2O
(W-1),
which
demonstrates
selectivity
anilines,
enabling
precise
production
various
azoxybenzenes,
symmetric/unsymmetric
azobenzenes,
nitrosobenzenes,
as
well
nitrobenzenes.
marks
instance
molecular
being
employed
for
four
distinct
through
aniline
oxidation.
A
combination
kinetic
measurements
stoichiometric
experiments
unveils
that
original
individual
among
many
can
potentially
arise
is
governed
conversion
intermediates
N-phenylhydroxylamine
nitrosobenzene
into
specific
procedures.
peroxotungstate
[W(O2)2(O)4-MeObpy]
(W-2)
was
isolated
reaction
W-1
with
H2O2.
combined
experimental
results
density
functional
theory
(DFT)
investigations
unraveled
W-2
critical
generating
both
key
providing
H-bonding
network
catalytic
systems.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14837 - 14843
Опубликована: Янв. 1, 2024
The
syntheses
of
first,
extremely
sensitive
donor-stabilized
monomeric
bismuthanylboranes
D·BH
2
Bi(SiMe
3
)
(D
=
NHC,
DMAP)
and
the
bismuthanylgallane
IDipp·GaH
are
presented
representing
unique
element
combinations
bismuth
triels.
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(4)
Опубликована: Янв. 13, 2023
Abstract
Heavier
main‐group
element‐catalyzed
reactions
provide
an
increasingly
attractive
tool
to
perform
transformations
mimicking
the
behaviors
of
transition
metal
catalysts.
Recently,
Magre
and
Cornella
reported
a
Bi‐catalyzed
synthesis
aryl
sulfonyl
fluorides,
which
involves
fundamental
organometallic
step
SO
2
insertion
into
Bi−Ph
bond.
Our
theoretical
studies
reveal
that
i)
ability
hypervalent
coordination
Bi(III)
center
allows
facile
sphere
expansion
for
via
one
oxygen
atom;
ii)
high
polarity
bond
makes
Ph
migration
from
feasible.
These
features
enable
heavier
main
group
element
resemble
having
flexibility
ligand
association
dissociation.
Furthermore,
iii)
available
π
electron
pair
migrating
stabilizes
state
by
maintaining
interaction
with
during
migration.
The
insight
helps
us
better
understand
catalysis.
Organic Letters,
Год журнала:
2023,
Номер
25(24), С. 4546 - 4550
Опубликована: Июнь 8, 2023
Few
studies
have
been
performed
on
allenyl
monofluorides,
especially
aryl-substituted
frames,
due
to
concerns
about
their
stability.
Here
we
report
a
copper-catalyzed
regioselective
synthesis
of
such
structures
with
inexpensive
and
accessible
aryl
boronic
esters
under
mild
conditions.
Arylated
monofluorides
were
stable
enough
be
isolated
easily
converted
various
other
fluorine-containing
blueprints.
Preliminary
asymmetric
attempts
demonstrate
that
the
reaction
could
proceed
via
selective
β-fluorine
elimination
process.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(12)
Опубликована: Дек. 22, 2023
Abstract
A
general
synthesis
and
the
characterization
of
novel
alkyl‐substituted
NHC‐stabilized
pnictogenylboranes
NHC
⋅
BH
2
ER
(NHC=N‐heterocyclic
carbene,
E=P,
As;
R
=Me
,
Ph
t
BuH,
Cy
(SiMe
3
)
are
reported.
These
compounds
were
reacted
with
Ni(CO)
4
to
corresponding
complexes
type
[(NHC
)Ni(CO)
]
determine
their
donor
strength
by
Tolman
Electronic
Parameters
(TEPs)
steric
demand
as
ligands
compared
classical
phosphines,
superbasic
phosphines
other
commonly
applied
systems.
The
results
show
that
pnictogenyltrielanes
can
be
considered
being
highly
basic,
while
influence
depends
strongly
on
organic
residues
well
attached
{BH
}
moiety.
Although
weaker
than
used
in
classified
similar
NHCs.
electronic
properties
easily
modified
alkyl
substitution
evident
from
TEP
trends.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 15, 2024
Chiral
Cp
x
Rh-catalyzed
enantioselective
sp
2
C–H
bond
activation/annulation
reactions
give
S-stereogenic
poly-heterocyclic
sulfoximines
in
up
to
99%
ee.
The
tricyclic
products
can
be
converted
into
10-membered
upon
oxidation.
Angewandte Chemie,
Год журнала:
2023,
Номер
136(8)
Опубликована: Ноя. 22, 2023
Abstract
Whereas
indications
of
radical
reactivity
in
bismuth
compounds
can
be
traced
back
to
the
19
th
century,
preparation
and
characterization
both
transient
persistent
bismuth‐radical
species
has
only
been
established
recent
decades.
These
advancements
led
emergence
field
chemistry,
mirroring
progress
seen
for
other
main‐group
elements.
The
seminal
fundamental
studies
this
area
have
ultimately
paved
way
development
catalytic
methodologies
involving
intermediates,
a
promising
approach
that
remains
largely
untapped
broad
landscape
synthetic
organic
chemistry.
In
review,
we
delve
into
milestones
eventually
present
state‐of‐the‐art
Our
focus
aims
at
outlining
intrinsic
discoveries
inorganic/organometallic
chemistry
contextualizing
their
practical
applications
synthesis
catalysis.
