Ni-Catalyzed Enantioselective Desymmetrization: Development of Divergent Acyl and Decarbonylative Cross-Coupling Reactions
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 14, 2025
Ni-catalyzed
asymmetric
reductive
cross-coupling
reactions
provide
rapid
and
modular
access
to
enantioenriched
building
blocks
from
simple
electrophile
precursors.
Reductive
coupling
that
can
diverge
through
a
common
organometallic
intermediate
two
distinct
families
of
products
are
particularly
versatile
but
underdeveloped.
Here,
we
describe
the
development
bis(oxazoline)
ligand
enables
desymmetrization
meso-anhydrides.
When
secondary
benzylic
electrophiles
employed,
doubly
stereoselective
acyl
proceeds
give
ketone
with
catalyst
control
over
three
newly
formed
stereogenic
centers.
Alternatively,
use
primary
alkyl
halides
in
presence
an
additional
halogen
atom
transfer
results
decarbonylative
alkylation
β-alkyl
acids.
Analysis
reaction
rates
for
range
both
catalysts
substrates
supports
notion
tuning
different
activation
steps
is
required
enhanced
performance.
These
studies
illustrate
how
design
Ni-acyl
either
or
highlight
dual
systems
be
used
engage
unactivated
coupling.
Язык: Английский
Cryogenic Organometallic Carbon–Fluoride Bond Functionalization with Broad Functional Group Tolerance
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 6, 2025
The
unique
properties
of
fluorinated
organic
compounds
have
received
intense
interest
and
conquered
a
myriad
applications
in
the
chemical
pharmaceutical
sciences.
Today,
an
impressive
range
alkyl
fluorides
are
commercially
available,
there
many
practical
methods
to
make
them
exist.
However,
unmatched
stability
inertness
C–F
bond
largely
limited
its
synthetic
value,
which
is
very
different
from
widely
accepted
utility
chlorides,
bromides,
iodides
that
serve
everyday
as
"workhorse"
building
blocks
countless
carbon–carbon
forming
reactions.
This
study
demonstrates
high-yielding
functionalization
under
mild
conditions,
i.e.,
at
temperatures
low
−78
°C,
short
reaction
times
with
unconventional
chemoselectivity.
Cryogenic
Csp3–F
cleavage
using
fluorophilic
organoaluminum
together
fast
nucleophile
transfer
intermediate
ate
complexes
forge
bonds
unactivated
primary,
secondary,
tertiary
alike.
method,
exploits
Al–F
thermodynamic
driving
force,
highly
selective
toward
functionalization,
whereas
other
functional
groups
including
chloride,
bromide,
iodide,
aryl
halide,
alkenyl,
alkynyl,
difluoroalkyl,
trifluoromethyl,
ether,
ester,
hydroxyl,
acetal,
heteroaryl,
nitrile,
nitro,
amide
tolerated,
unexpected
reversal
long-standing
main
group
organometallic
halide
cross-coupling
reactivity
compatibility
patterns.
As
result,
strongest
single
chemistry
can
now
be
selectively
targeted
arylation,
alkylation,
alkenylation,
alkynylation
reactions
used
late-stage
complementary
currently
available
methods.
Язык: Английский
Rhodium- and Iridium-Catalyzed (Enantioselective) Fluoroamidation of gem-Difluoroalkenes via Chelation Assistance
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 6555 - 6562
Опубликована: Апрель 7, 2025
Язык: Английский
Effect of Ligand Backbone on the Electrochemical Hydrogen Evolution Reaction and Hydrogen-Atom-Transfer Reactivity Using a Nickel Polypyridine Quinoline Complex
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Redox-active
quinoline-containing
[NiII(2PyN2Q)
(H2O)]2+
complex
(1)
has
been
developed
for
the
electrocatalytic
(e)
hydrogen
evolution
reaction
(HER)
in
presence
of
organic
acids
and
water
hydrogen-atom-transfer
(HAT)
with
styrene
acids.
Complex
1
shows
promising
e-HER
performance
up
to
pH
9.
It
exhibits
a
stepwise
(E)ECEC
mechanism
AcOH,
while
potential-dependent
bimolecular
homolytic
pathway
CEEC
is
operative
p-toluene
sulfonic
acid
during
e-HER.
The
one-
two-electron-reduced
species
are
characterized
by
spectro-electrochemistry,
optical,
EPR
studies.
Moreover,
inverse
kinetic
isotope
effect
(KIE
=
0.83)
between
AcOH
d4-AcOH
e-HAT
hydro-functionalization
using
catalyst
possibly
suggests
involvement
nickel
hydride
species.
reactivity
have
compared
redox-inactive
[NiII(N4Py)(H2O)]2+
(2),
demonstrating
prominent
quinoline
pyridine
e-HAT.
proposed
well
supported
DFT
Язык: Английский
Silver-Catalyzed (Z)-β-Fluoro-vinyl Iodonium Salts from Alkynes: Efficient and Selective Syntheses of Z-Monofluoroalkenes
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15672 - 15680
Опубликована: Июнь 3, 2024
Monofluoroalkenes
are
stable
and
lipophilic
amide
bioisosteres
used
in
medicinal
chemistry.
However,
efficient
stereoselective
methods
for
synthesizing
Z-monofluoroalkenes
underdeveloped.
We
envisage
(Z)-β-fluoro-vinyl
iodonium
salts
(Z-FVIs)
as
coupling
partners
the
diverse
synthesis
of
Z-monofluoroalkenes.
Disclosed
herein
is
development
application
a
silver(I)-catalyzed
process
accessing
broad
scope
(Z)-FVIs
with
exclusive
Z-stereoselectivity
regioselectivity
from
alkynes
single
step.
Experimental
computational
studies
provide
insight
into
mechanism
catalytic
cycle
role
silver(I)
catalyst,
reactivity
explored
through
several
stereospecific
derivatizations.
Язык: Английский
Nickel-Catalyzed Asymmetric Hydroalkylation of Alkenyl Fluorides
Synfacts,
Год журнала:
2024,
Номер
20(07), С. 0724 - 0724
Опубликована: Июнь 14, 2024
Key
words
alkenyl
fluorides
-
asymmetric
catalysis
hydroalkylation
nickel
radical
group
transfer
Язык: Английский
Chemoselective Hydroheteroarylation of Alkenes via Photoredox-Neutral Proton- and BF3-Mediated Electron Transfer
Organic Letters,
Год журнала:
2024,
Номер
26(36), С. 7707 - 7712
Опубликована: Авг. 28, 2024
Herein,
we
have
developed
a
complementary
entry
to
enable
hydroheteroarylation
of
alkenes
involving
basically
photoredox
dearomatizative
heterocyclic
carbon
radical
formation
through
acid-coupled
electron
transfer
followed
by
Giese
addition.
While
protonic
solvent
and
thiophenol
additive
enabled
two
molecular
hydroheteroarylations
alkenes,
the
nonproton
environment
with
BF
Язык: Английский
Atroposelective Three-Component (Fluoro)methylative Alkylation of Terminal Alkynes
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 63 - 71
Опубликована: Дек. 13, 2024
The
development
of
synthetic
methods
for
the
selective
installation
methyl
and
fluoromethyl
groups
is
highly
desired
due
to
their
critical
role
in
drug
development.
While
significant
advances
have
been
made
methylation
difluoromethylation
aromatic
compounds,
catalytic
atroposelective
(fluoro)methylative
functionalization
alkynes
forge
axially
chiral
alkenes
remains
underexploited.
Herein,
we
report
an
enantioselective
cross-electrophile
strategy
efficient
1,2-carbo-(fluoro)methylation
with
two
different
alkyl
halides
via
nickel
catalysis.
By
integrating
a
one-electron
radical
process
two-electron
organometallic
process,
this
protocol
employs
simple
catalyst
effectively
discriminate
between
secondary
tertiary
(fluoro)methyl
alkyne
difunctionalization.
This
demonstrates
good
compatibility
activated
secondary/tertiary
bromides,
terminal
alkynes,
halides,
permitting
straightforward
synthesis
broad
range
synthetically
valuable
(fluoro)methyl-substituted
high
chemo-,
regio-,
trans-,
atropo-selectivity.
Preliminary
mechanistic
studies
provide
insight
into
potential
reaction
pathway.
Язык: Английский