ChemCatChem,
Год журнала:
2021,
Номер
13(7), С. 1738 - 1742
Опубликована: Янв. 28, 2021
Abstract
Herein,
we
report
a
general
and
efficient
method
for
the
palladium‐catalyzed
remote
C(sp
2
)−H
difluoroalkylation
of
N
‐aryloxazolidinone
derivatives
with
commercially
available
difluoroalkyl
bromide.
This
tolerates
wide
range
functional
groups
26
examples
in
up
to
96
%
yields.
Moreover,
it
proceeds
complete
para
‐selectivity.
Preliminary
mechanistic
studies
indicated
that
single
electron
transfer
process
likely
involved
this
transformation.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июль 16, 2021
Installation
of
fluorine
into
pharmaceutically
relevant
molecules
plays
a
vital
role
in
their
properties
biology
or
medicinal
chemistry.
Direct
difunctionalization
alkenes
and
1,3-dienes
to
achieve
fluorinated
compounds
through
transition-metal
catalysis
is
challenging,
due
the
facile
β-H
elimination
from
Csp3‒[M]
intermediate.
Here
we
report
cobalt-catalyzed
regioselective
difluoroalkylarylation
both
activated
unactivated
with
solid
arylzinc
pivalates
difluoroalkyl
bromides
cascade
Csp3‒Csp3/Csp3‒Csp2
bond
formation
under
mild
reaction
conditions.
Indeed,
wide
range
functional
groups
on
bromides,
olefins,
as
well
(hetero)arylzinc
are
tolerated
by
cobalt-catalyst,
thus
furnishing
three-component
coupling
products
good
yields
high
regio-
diastereoselectivity.
Kinetic
experiments
comparing
conventional
halides
highlight
unique
reactivity
these
organozinc
pivalates.
Mechanistic
studies
strongly
support
that
involves
direct
halogen
atom
abstraction
via
single
electron
transfer
situ
formed
cobalt(I)
species,
realizing
Co(I)/Co(II)/Co(III)
catalytic
cycle.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Июнь 8, 2022
Abstract
C‐aryl
glycosides
are
popular
basic
skeletons
in
biochemistry
and
pharmaceutical
chemistry.
Herein,
ruthenium‐catalyzed
highly
stereo‐
site‐selective
ortho
‐
meta
‐C
Ar
−H
glycosylation
is
described.
A
series
of
pyranosides
furanosides
were
synthesized
by
this
method.
The
strategy
showed
good
substrate
scope,
various
N
‐heterocyclic
directing
groups
compatible
with
the
reaction
system.
mechanistic
study
suggested
that
key
pathway
might
involve
oxidative
addition/reduction
elimination,
whereas
aryl
‐C−H
was
mediated
σ
‐activation.
Density
functional
theory
calculations
also
high
stereoselectivity
due
to
steric
hindrance.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(6), С. 1742 - 1775
Опубликована: Янв. 1, 2022
This
review
focuses
on
the
advances
in
transition-metal
catalyzed
reactions
with
fluorinated
building
blocks
via
directed
C–H
bond
activation
for
construction
of
diverse
organic
molecules
an
insight
into
probable
mechanistic
pathway.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(15), С. 4192 - 4208
Опубликована: Янв. 1, 2022
In
this
review,
we
summarize
the
state-of-the-art
advances
in
difluoromethylation
of
heterocycles
via
a
radical
process
over
past
few
years
(2018
to
early
2022).
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(47), С. 9298 - 9315
Опубликована: Янв. 1, 2023
Recent
advances
on
non-precious
metal-catalysed
fluorination,
difluorimethylation,
trifluoromethylation,
and
perfluoroalkylation
of
N-heteroarenes
is
presented.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(52)
Опубликована: Ноя. 10, 2023
Photoelectrochemistry
is
becoming
an
innovative
approach
to
organic
synthesis.
Generally,
the
current
photoelectrocatalytic
transformations
suffer
from
limited
reaction
type,
low
conversion
efficiency
and
poor
stability.
Herein,
we
develop
efficient
stable
photoelectrode
materials
using
metal
oxide
protective
layer,
with
a
focus
on
achieving
regioselective
activation
of
amine
compounds.
Notably,
our
photoelectrochemistry
process
implemented
under
mild
conditions
does
not
involve
any
directing
groups,
transition
metals
or
oxidants.
The
results
demonstrate
that
beyond
photocatalysis
electrocatalysis,
photoelectrocatalysis
exhibits
high
efficiency,
remarkable
repeatability
good
functional
group
tolerance,
highlighting
its
great
potential
for
applications.
ACS Catalysis,
Год журнала:
2023,
Номер
13(11), С. 7310 - 7321
Опубликована: Май 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
