ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 907 - 916
Опубликована: Дек. 30, 2024
Catalytic
reactions
involving
1,n-metal
migration
provide
a
powerful
approach
for
the
synthesis
of
complex
molecular
skeletons
from
simple
precursors
through
activation
unreactive
bonds.
In
this
work,
nickel-catalyzed
3,3-disubstituted
1-silaindanes,
silicon
analogues
valuable
indanes,
was
developed
by
reaction
1,5-nickel
via
C–H
bond
and
1,4-nickel
C–Si
activation.
It
found
that
not
only
enabled
at
remote
position
but
also
controlled
regioselectivity
subsequent
alkene
insertion.
The
detailed
mechanism
investigated
conducting
deuterium
labeling
experiments
DFT
calculations.
results
obtained
here
demonstrate
high
potential
catalytic
nickel
migrations
activations
useful
cyclic
organosilicon
compounds.
The
transition
metal-catalyzed
coupling
reaction
has
renewed
the
role
of
ester
as
an
electrophilic
partner.
In
this
context,
we
describe
a
synergistic
Ni/Zn-catalyzed
formal
transesterification
but-3-enyl
esters
with
tetrahydrofuran
and
alkyl
iodides
to
give
4-alkoxylbutyl
esters.
aromatic
aliphatic
are
both
competent
electrophiles
thus
broaden
substrate
scope
in
reactions,
because
previously
reported
work
were
strictly
limited
ones.
Mechanistic
studies
reveal
that
C(acyl)-O
bond
or
even
more
inert
C(alkyl)-O
could
be
cleaved
under
nickel
catalysis.
Two
catalytic
cycles
proposed,
which
represent
new
pathway
versus
traditional
transesterification.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
We
herein
describe
the
nickel-catalyzed
C2–H
alkylation
of
benzothiazoles
with
unactivated
α-olefins
by
using
Ni(IPr*OMe)[P(OEt)3]Br2/Mg
catalytic
system
in
which
a
variety
linear
alkylated
high
regioselectivity
were
formed
under
mild
reaction
conditions.
This
transformation
showed
good
compatibility
to
bearing
various
functional
groups,
such
as
esters,
acetals,
silyl
ethers,
amines,
silanes,
and
boronate
esters.
Furthermore,
this
is
also
suitable
other
typical
N-heteroarenes
including
thiazoles,
benzimidazoles,
quinazolones,
uracils,
pyridines,
caffeines,
indoles.
Thus,
work
provides
rapid
access
diverse
step
atom
economy.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 5, 2025
The
β-H
elimination
is
a
crucial
elementary
step
in
transition-metal
catalysis,
but
controlling
the
stereochemistry
of
this
process
has
been
underdeveloped.
limited
works
reported
so
far
have
only
focused
on
creating
axial
chirality
allenes,
and
no
report
able
to
build
central
using
asymmetric
elimination.
In
study,
we
Trost
ligand-enabled
enantioselective
desymmetric
reaction
from
π-allyl-Pd.
This
transformation
provides
rapid
access
cyclohexenes
bearing
C4-remoted
stereocenter,
total
synthesis
(-)-oleuropeic
acid
(-)-7-hydroxyterpineol
demonstrated.
Computational
studies
shown
that
rate-determining
step,
non-covalent
interactions
between
amide
moiety
ligand
benzene
cyclohexane
moieties
substrate
play
key
role
stereocontrol
during
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 9, 2025
Migratory
functionalization
of
C-H
bonds
through
metal
migration
from
carbon
to
under
transition
catalysis
is
a
process
significant
academic
and
industrial
interest.
Herein,
palladium-catalyzed
migratory
cyclization
α-bromoalkene
derivatives
ArXCBr=CH2,
in
which
X
denotes
phosphorus
(P(O)R),
silicon
(SiR2),
sulfur
(SO2),
(C(O)),
nitrogen
(NTs),
or
oxygen-based
moiety,
affording
various
benzoheterocyclic
compounds
has
been
developed.
Mechanistic
investigations
have
demonstrated
that
the
reaction
proceeds
an
unexpected
cascade,
with
trans-1,2-palladium
between
sp2
carbons
being
key
step
catalytic
cycle.
To
best
our
knowledge,
this
type
not
reported
previously.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
Comprehensive
Summary
Radical
hydrogenation
facilitated
by
metal
(Fe,
Co,
Mn,
etc
.)
hydride‐mediated
hydrogen
atom
transfer
(
m
HAT)
has
emerged
as
a
powerful
technique
in
organic
synthesis.
However,
nickel‐hydride
(NiH)
catalyzed
radical
remained
largely
unexplored.
Herein,
we
develop
NiH
catalytic
system
that
achieves
the
of
enamides
high
efficiency.
This
strategy
stands
out
for
its
ability
to
hydrogenate
challenging
quinolines
at
room
temperature,
avoiding
catalyst
poisoning
and
deactivation
their
products.
Furthermore,
deuteration
alkenes
was
achieved
with
rates
(up
>
99%),
underscoring
potential
synthesis
deuterium‐containing
molecules.
The
example
of
iron-catalyzed
alkenes
migratory
silylation
and
transposition
has
been
demonstrated,
affording
a
tunable
approach
to
synthesize
thermodynamically
stable
allylsilanes
internal
with
high
efficiency
regioselectivity.
These
reactions
showcase
several
advantageous
features,
including
good
functional
group
tolerance,
excellent
regioselectivity,
broad
substrate
scope,
scalability
gram-scale
synthesis,
late-stage
functionalization
bio-relevant
molecules.
Furthermore,
the
relay
catalytic
mechanism
silylation,
involving
both
iron-silyl
iron-hydride
intermediates,
provides
valuable
insights
into
coupling
reactions,
opening
new
avenues
for
development
novel
transformations
under
iron
catalysis.
Abstract
Complementary
to
the
design
of
a
single
structurally
complex
chiral
ligand
promote
each
step
in
transition‐metal
catalysis,
multiligand
relay
catalysis
through
dynamic
exchange
with
catalytic
cycle
promoted
by
its
best
provides
an
attractive
approach
enhance
whole
reaction
reactivity
and
selectivity.
Herein,
regio‐
enantioselective
NiH‐catalyzed
migratory
hydroarylation
process
simple
combination
chain‐walking
asymmetric
arylation
ligand,
producing
high‐value
α
‐(hetero)aryl‐substituted
amines
their
derivatives
under
mild
conditions,
is
reported.
The
potential
synthetic
applications
this
transformation
are
demonstrated
concise
synthesis
(
S
)‐nicotine
CDK8
inhibitor.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2068 - 2072
Опубликована: Март 1, 2024
An
efficient
copper-catalyzed
selective
fluoromethylthiolation
of
an
inert
δ-C(sp3)–H
bond
in
sulfonamides
was
reported.
In
the
presence
a
copper
catalyst
and
PhSO2SRf,
radical
generated
through
1,5-hydrogen
atom
transfer
(HAT)
sufficiently
trapped
by
instead
copper,
which
prevalent
metal-catalyzed
radical-relay
processes,
incorporating
fluoromethylthio
group
into
molecules.
The
general
substrate
scope
mild
conditions
endowed
method
with
wide
potential
applications
pharmaceuticals
agrochemicals.
