Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
Ni-catalyzed
multicomponent
cross-couplings
have
emerged
as
a
powerful
strategy
for
efficiently
constructing
complex
molecular
architectures
from
diverse
array
of
organic
halides.
Despite
its
potential,
selectively
forming
multiple
chemical
bonds
in
single
operation,
particularly
the
realm
cross-electrophile
coupling
catalysis,
remains
significant
challenge.
In
this
study,
we
developed
consecutive
open-shell
reductive
Ni
enabling
formation
two
geminal
C(sp
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13451 - 13496
Опубликована: Авг. 26, 2024
Alcohols
are
abundant
with
versatile
structural
variety
and
have
ample
use
as
pivotal
functional
groups
in
numerous
organic
processes.
Because
of
their
frequent
occurrence
enumerable
natural
products,
bioactive
molecules,
medicinal
components,
alcohol
functionalities
provide
a
promising
scope
research
to
advance
the
operational
diversity
for
improving
clinical
success.
Recent
years
witnessed
design
modern
C–C
C–heteroatom
bond-forming
approaches
easily
accessible
commercially
available
unactivated
aliphatic
alcohols
native
adaptive
sp3
handles,
hence
offering
groundbreaking
transformative
pathways
functionalization
complex
molecular
architectures.
The
judicial
application
appropriate
activating
generate
alkyl
radical
from
through
C–O
bond
fragmentation
employ
it
potential
alkylating
agent
unfolds
unique
synthetic
strategies,
thereby
replacing
obvious
requirement
halides.
This
review
elaborately
discusses
recent
trends
regarding
using
C(sp3)-centered
various
chemical
transformations
by
exploiting
different
activation
modes
disrupter
under
photoredox
catalysis.
presentation
is
organized
nature
scaffolds,
kind
formation,
progress
achieved
this
domain
since
original
discovery
providing
illustrative
examples
mechanistic
details,
focus
on
difficulties
future
prospects.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
The
direct
synthesis
of
C(sp3)-rich
architectures
is
a
driving
force
for
innovation
in
synthetic
organic
chemistry.
Such
scaffolds
impart
beneficial
properties
onto
drug
molecules
that
correlate
with
greater
clinical
success.
Consequently,
there
strong
impetus
to
develop
new
methods
by
which
access
sp3-rich
from
commercial
feedstocks,
such
as
alkenes.
Herein,
we
report
three-component
aminoalkylation
reaction
utilizes
the
principles
triple
radical
sorting
regioselectively
add
N-centered
and
C-centered
radicals
across
This
process
relies
upon
photoredox
catalysis
transform
alkyl
bromides
reductively
activated
precursors
into
high-energy
species
redox-neutral
fashion.
A
broad
scope
coupling
partners
demonstrated,
multiple
applications,
including
facile
syntheses
pharmacophoric
substituted
N-heterocycles.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
general
method
for
accessing
α,β-unsaturated
ketones
through
visible-light
or
sunlight
photoredox-catalyzed
β-selective
acylation
of
alkenes
has
been
developed.
Nature Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Methyltransferases
are
a
broad
class
of
enzymes
that
catalyse
the
transfer
methyl
groups
onto
wide
variety
substrates
and
functionalities.
In
their
most
striking
variant,
bifunctional
methyltransferase-cyclases
both
group
alkenes
induce
cyclization
(methylcyclization).
Although
recent
years
have
seen
substantial
advances
in
methylation
alkenes,
especially
hydromethylation,
reactivity
demonstrated
by
nature
has
yet
to
be
developed
into
synthetically
viable
method.
Here
we
report
silver(I)-mediated
electrophilic
methylcyclization
rivals
selectivities
found
while
not
being
limited
inherent
substrate
specificity.
Our
method
benefits
from
use
commercial
reagents,
is
applicable
range
substrates,
including
heterocycles,
affords
unique
structures
difficult
access
via
conventional
synthetic
methods.
Furthermore,
computational
studies
been
utilized
unravel
underlying
mechanism
ultimately
support
stepwise
cationic
reaction
pathway
with
rate-limiting
methyltransfer.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
Ligand-to-metal
charge
transfer
(LMCT)
excitation
has
emerged
as
a
potent
strategy
for
the
selective
generation
of
heteroatom-centered
radicals,
yet
its
full
potential
in
modulating
open-shell
radical
pathways
remains
underexplored.
Here,
we
present
photocatalytic
methylative
cross-coupling
reaction
that
capitalizes
on
synergistic
interplay
between
LMCT
and
Ni
catalysis,
enabling
use
tert-butanol
an
efficient
benign
methylating
reagent.
The
electron-deficient
ligand
2,6-ditrifluoromethyl
benzoate
facilitates
Ce(IV)-mediated
bond
scission
tert-butanol,
generating
methyl
is
subsequently
captured
by
catalytic
cycle
to
form
C-CH3
bonds.
Under
mild
conditions,
this
affords
methylation
sp3
carbons
adjacent
carbonyls
sp2
centers,
demonstrating
broad
functional
group
tolerance
applicability
late-stage
functionalization
bioactive
molecules.
Additionally,
trideuteromethylative
coupling
can
be
facilely
achieved
using
commercial
tert-butanol-d10.
This
approach
circumvents
need
traditional
tert-butoxy
precursors,
such
peroxides,
while
strategically
pathway
favor
β-scission
suppress
unwanted
formation
solution.
Mechanistic
studies
reveal
plays
crucial
role
facilitating
generation,
supporting
concerted
Ce-OR
β-C-C
homolysis
mechanism,
further
evidenced
modulation
regioselectivity
alkoxy
radical-mediated
β-scission.
Organic Letters,
Год журнала:
2024,
Номер
26(23), С. 4893 - 4897
Опубликована: Июнь 5, 2024
Cobalt-catalyzed
metal
hydride
hydrogen
atom
transfer
(MHAT)
in
combination
with
photoredox
catalysis
has
emerged
as
a
powerful
synthetic
method,
owing
to
its
redox
nature
and
applicability
various
radical
precursors.
Herein,
we
describe
cross-radical
coupling
reaction
under
cobalt/photoredox
dual
catalysis.
MHAT
homolytic
substitution
(SH2)
processes
enabled
Markovnikov-selective
hydrobenzylation
of
di/trisubstituted
alkenes,
affording
products
quaternary
carbon
center
redox-neutral
manner.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(22), С. 16106 - 16113
Опубликована: Июнь 26, 2024
This
Synopsis
covers
recent
reports
of
metal-catalyzed
alkene
functionalizations
that
likely
involve
iterative
outer-sphere
reactions
in
which
the
substrate
reacts
directly
with
a
metal
ligand
instead
center
itself.
Traditional
hydride-catalyzed
this
latter
pathway
whereby
forms
part
sphere
(i.e.
an
inner-sphere
reaction).
In
contrast,
alkenes
do
not
ligate
so-called
and
react
ligand.
These
transformations
have
proved
crucial
for
synthesis
high
fraction
sp3
(Fsp3)
targets,
especially
hindered
fragment
couplings
relevance
to
natural
product
space.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14865 - 14871
Опубликована: Янв. 1, 2024
A
novel
photoinduced
Co/Ni-cocatalyzed
Markovnikov
hydroarylation
of
unactivated
alkenes
with
aryl
bromides
by
using
proton
as
a
hydrogen
source
has
been
developed
for
the
first
time.
