Synlett,
Год журнала:
2023,
Номер
35(08), С. 851 - 861
Опубликована: Ноя. 24, 2023
Abstract
Base
metal
catalyzed
C–H
activation
represents
a
highly
atom
economic
method
to
access
functionalized
molecules.
This
Account
will
focus
on
Ni-catalyzed
of
sp3-hybridized
carbon
atoms
with
particular
mechanism,
recent
applications,
challenges,
and
outlook
in
this
area.
primarily
mechanistic
work
from
2017–2023.1
Metal
Activation
2
Nickel-Catalyzed
sp3
3
Differences
between
Ni
Pd
4
Mechanistic
Considerations
5
Elementary
Steps
6
Directed
7
Choice
Directing
Group
8
Primary
9
Secondary
10
Tertiary
11
Conclusion
Outlook
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
146(1), С. 112 - 117
Опубликована: Дек. 28, 2023
Herein,
we
report
the
utilization
of
Ni–Ni
species
as
a
manifold
for
enabling
"ring-walking"
event
by
dynamic
translocation
metal
center
over
arene
backbone.
Experimental
and
computational
studies
support
occurring
via
1,2-hydride
shift.
The
synthetic
applicability
method
is
illustrated
in
series
C–C
bond
formations
that
occur
at
distal
C(sp2)–H
sites
simple
aryl
pivalates.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 1, 2024
Asymmetric
de
novo
synthesis
of
benzocyclobutenes
(BCBs)
via
catalytic
intermolecular
reaction
is
highly
desired
for
efficient
access
to
this
important
class
compounds,
yet
such
a
strategy
remains
unmet
challenge.
Here,
we
report
Pd/Pyrox-catalyzed
asymmetric
[2+2]
annulation
between
arylboronic
acids
and
functionalized
alkenes,
providing
an
unprecedented
protocol
various
enantio-enriched
BCBs
in
modular
versatile
manner
under
mild
conditions.
A
broad
substrate
scope
with
excellent
enantioselectivity
has
been
achieved
the
current
protocol.
The
isolation
characterization
key
chiral
palladacycle
intermediate,
together
DFT
calculations,
provides
strong
evidence
pathway
including
enantiodetermining
arylpalladation
step.
Herein,
we
report
the
utilization
of
Ni-Ni
species
as
a
manifold
for
enabling
“ring-walking”
event
by
dynamic
translocation
metal
center
over
arene
backbone.
Experimental
and
computational
studies
support
occurring
via
1,2-hydride
shift.
The
synthetic
applicability
method
is
illustrated
in
series
C–C
bond
for-mations
that
occur
at
distal
C(sp2)–H
sites
sim-ple
aryl
pivalates
We
reported
a
Pd/NBE
cooperative
catalyzed
ortho
C−H
methylation
and
trideuteromethylation
of
arylthianthrenium
salts,
enabling
the
efficient
synthesis
wide
variety
(trideutero)methylated
arenes
in
moderate
to
good
yields.
The
method
demonstrates
excel-lent
tolerance
towards
functional
groups,
scalability,
potential
extension
late-stage
functionalization
biorelevant
mole-cules.
In
combined
with
thianthrenation
arenes,
this
approach
provides
an
effective
for
site-selective
(trideutero)methylation
arenes.
Additionally,
reaction
represents
first
example
Catellani
involving
aryl
sul-fonium
salts.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(7)
Опубликована: Ноя. 6, 2023
Reaching
the
formidable
C-H
corners
has
been
one
of
top
priorities
organic
chemists
in
recent
past.
This
prompted
us
to
disclose
herein
a
vicinal
annulation
2-iodo
benzoates,
indoles,
and
carbazoles
with
N-embedded
1,6-enynes
through
7-/8-membered
palladacycles.
The
relay
does
not
require
assistance
any
directing
group,
leading
multicyclic
scaffolds,
which
are
readily
diversified
an
array
adducts
(with
new
functional
tethers
and/or
three
contiguous
stereocenters),
we
showcase
rare
benzylic
mono-oxygenation.
Polymer
electrolyte
(PEs)
based
solid-state
lithium
metal
batteries
(SSLMBs)
featuring
LiNi0.8Co0.1Mn0.1O2
(NCM811)
cathodes
offer
high
energy
density
and
safety.
However,
their
development
is
hampered
by
the
poor
anti-oxidation
ability
severe
interfacial
reactions
between
PEs
NCM811
cathode.
Herein,
butanesultone-based
polymer
electrolytes
(PBS-PEs)
were
synthesized
via
ring-opening
polymerization,
with
different
terminal
groups
tailored
to
optimize
interface
compatibility.
The
electron-withdrawing
properties
of
sulfonate
readily
complex
nickel
atoms,
enhancing
resistance
PEs.
Furthermore,
PBS-PEs
containing
-OCH3
trifluoromethanesulfonate
groups,
exhibit
superior
electrochemical
performance
compared
those
-OH
groups.
These
variants
a
wide
stability
window
5.1
V
(vs.
Li+/Li)
ionic
conductivity
reaching
up
1.25×10-3
S
cm-1
at
25°C.
improved
compatibility
exhibiting
good
capacity
retention
80%
after
150
cycles
current
2
C
when
charged
4.6
V.
Thus,
this
study
not
only
introduces
novel
for
pairing
high-voltage
cathodes,
but
also
advances
application
cathode
material
in
high-energy
SSLMBs.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 1, 2024
Abstract
Asymmetric
de
novo
synthesis
of
benzocyclobutenes
(BCBs)
via
catalytic
intermolecular
reaction
is
highly
desired
for
efficient
access
to
this
important
class
compounds,
yet
such
a
strategy
remains
unmet
challenge.
Here,
we
report
Pd/Pyrox‐catalyzed
asymmetric
[2+2]
annulation
between
arylboronic
acids
and
functionalized
alkenes,
providing
an
unprecedented
protocol
various
enantio‐enriched
BCBs
in
modular
versatile
manner
under
mild
conditions.
A
broad
substrate
scope
with
excellent
enantioselectivity
has
been
achieved
the
current
protocol.
The
isolation
characterization
key
chiral
palladacycle
intermediate,
together
DFT
calculations,
provides
strong
evidence
pathway
including
enantiodetermining
arylpalladation
step.
Synlett,
Год журнала:
2023,
Номер
35(08), С. 851 - 861
Опубликована: Ноя. 24, 2023
Abstract
Base
metal
catalyzed
C–H
activation
represents
a
highly
atom
economic
method
to
access
functionalized
molecules.
This
Account
will
focus
on
Ni-catalyzed
of
sp3-hybridized
carbon
atoms
with
particular
mechanism,
recent
applications,
challenges,
and
outlook
in
this
area.
primarily
mechanistic
work
from
2017–2023.1
Metal
Activation
2
Nickel-Catalyzed
sp3
3
Differences
between
Ni
Pd
4
Mechanistic
Considerations
5
Elementary
Steps
6
Directed
7
Choice
Directing
Group
8
Primary
9
Secondary
10
Tertiary
11
Conclusion
Outlook
