ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4450 - 4459
Опубликована: Фев. 28, 2025
Enantioselective
electrocatalyzed
C–H
activations
have
emerged
as
a
transformative
platform
for
the
assembly
of
value-added
chiral
organic
molecules.
Despite
recent
progress,
construction
multiple
C(sp3)-stereogenic
centers
via
C(sp3)–C(sp3)
bond
formation
has
thus
far
proven
to
be
elusive.
In
contrast,
we
herein
report
an
annulative
activation
strategy,
generating
Fsp3-rich
molecules
with
high
levels
diastereo-
and
enantioselectivity.
κ2-N,O-oxazoline
preligands
were
effectively
employed
in
enantioselective
cobalt(III)-catalyzed
reactions.
Using
DFT-derived
descriptors
regression
statistical
modeling,
performed
parametrization
study
on
modularity
preligands.
The
resulted
model
describing
ligands'
selectivity
characterized
by
key
steric,
electronic,
interaction
behaviors.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 16, 2024
The
advancement
in
electrochemical
techniques
has
unlocked
a
new
path
for
achieving
unprecedented
oxidations
and
reductions
of
aryl
radical
precursors
controlled
selective
manner.
This
approach
facilitates
the
construction
aromatic
carbon-carbon
carbon-heteroatom
bonds.
In
light
green
merits
growing
importance
this
technique
chemistry,
review
aims
to
provide
an
overview
recent
advance
generation
radicals
organized
by
precursor
type,
with
focus
on
substrate
scope,
limitation,
underlying
mechanism,
thereby
inspiring
future
work
generation.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6652 - 6657
Опубликована: Июль 26, 2024
We
report
a
visible-light-promoted
cyclization/sulfonylation
cascade
of
N-heterocycles
with
thianthrenium
salts
using
DABSO
as
the
SO2
surrogate.
This
method
features
excellent
functional
group
tolerance,
wide
substrate
scope,
and
late-stage
elaboration
bioactive
relevant
molecules.
Mechanistic
investigations
reveal
that
photoactive
electron
donor–acceptor
(EDA)
complexes
between
DABCO
are
capable
generation
aryl
radicals,
which
induce
following
insertion
by
attacking
DABSO,
thus
triggering
key
radical
cyclization
step.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
Abstract
Sulfonium
salts
are
typically
bench‐stable
and
readily
available
reagents
that
showcase
diverse
chemical
reactivities.
Owing
to
these
synthetically
valuable
features,
sulfonium
salt
chemistry
has
witnessed
considerable
momentum
over
the
past
decades.
Particularly,
merger
of
electrosynthesis
enabled
utilization
electric
current
in
place
cost‐intensive
hazardous
redox
agents
maximize
attractive
characteristics
salts.
Additionally,
electrochemistry
allowed
chemists
dial
desired
potential,
offering
selective
access
target
products
otherwise
unattainable
by
either
thermal
or
photochemical
manifolds.
These
advantages
led
major
advances
chemistry.
Thus,
we,
herein,
provide
an
overview
early
pioneering
findings
recent
progress
devoted
organic
associated
with
until
December
2024,
aiming
stimulate
future
this
rapidly
evolving
arena.
Organic Letters,
Год журнала:
2024,
Номер
26(30), С. 6324 - 6329
Опубликована: Июль 22, 2024
Direct
functionalization
of
azobenzenes
provides
an
approach
to
obtaining
valuable
molecules
in
synthetic
chemistry.
However,
efficient
method
for
the
cleavage
N═N
bond
azobenzenes,
which
is
a
key
process
this
transformation,
still
lacking.
We
herein
disclose
electrochemical
reduction-induced
cyclization
with
aldehydes
via
cleavage.
This
proceeds
well
absence
any
transition
metals
or
external
chemical
oxidants,
leading
formation
N-protected
benzimidazoles
moderate
good
yields.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(46)
Опубликована: Авг. 28, 2024
Abstract
An
electrochemical
radical
cyclization
of
o
‐aminyl
azobenzenes
via
N
‐centered
generation
has
been
developed
for
the
synthesis
benzotriazoles.
The
bearing
a
sulfonyl
protection
on
amine
readily
proceeds
in
absence
any
external
transition
metal
catalyst
or
chemical
oxidant,
and
exhibits
good
tolerance
towards
functional
groups.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 13, 2024
Abstract
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel‐catalyzed
system
that
facilitates
various
deuterium‐labeled
through
hydrodeuteroalkylation
d2‐labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
2
O
as
source
via
single‐step
pH‐dependent
hydrogen
isotope
exchange
(HIE).
Our
method
allows
for
high
incorporation,
offers
precise
control
over
site
insertion
within
an
chain.
This
technique
proves
to
be
invaluable
compounds,
especially
those
relevance.
Chemical Communications,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
An
efficient
redox-neutral
palladium-catalyzed
system
has
been
developed
to
introduce
indole
and
pyrrole
various
bioactive
molecules
via
late-stage
aryl
C–H
activation,
providing
a
robust
tool
explore
structure–activity
relationships
(SARs).
