Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Фев. 25, 2023
Abstract
Asymmetric
ring-opening
of
7-oxabenzonorbornadienes
is
achieved
via
Co-catalyzed
indole
C–H
functionalization.
The
utilization
chiral
Co-catalyst
consisting
a
binaphthyl-derived
trisubstituted
cyclopentadienyl
ligand
resulted
in
high
yields
(up
to
99%)
and
excellent
enantioselectivity
(>99%
ee)
for
the
target
products
with
tolerance
diverse
functional
groups.
Opposite
diastereoselectivities
are
obtained
or
Cp*CoI
2
CO.
Combined
experimental
computational
studies
suggest
β
-oxygen
elimination
being
selectivity-determining
step
reaction.
Meanwhile,
reactions
7-azabenzonorbornadiene
could
also
be
executed
diastereodivergent
manner.
Organic Letters,
Год журнала:
2016,
Номер
18(24), С. 6320 - 6323
Опубликована: Дек. 5, 2016
A
cobalt(III)-catalyzed
α-fluoroalkenylation
of
different
arenes
with
readily
available
gem-difluorostyrenes
has
been
realized
under
mild
and
redox-neutral
conditions.
This
reaction
occurs
via
a
C–H
activation
pathway
offers
step-economical
access
to
various
1,2-diaryl-substituted
monofluoroalkenes
in
excellent
Z
selectivity
moderate
yields.
ACS Catalysis,
Год журнала:
2017,
Номер
7(7), С. 4592 - 4596
Опубликована: Июнь 5, 2017
A
procedure
for
the
direct
mechanochemical
rhodium(III)-catalyzed
C–H
bond
amidation
of
arenes
with
1,4,2-dioxazol-5-ones
as
nitrogen
source
has
been
developed.
The
transformation
proceeds
under
solventless
conditions
and
does
not
require
additional
heating.
corresponding
ortho
amidated
products
are
formed
in
high
yields
shorter
reaction
times
than
solution.
Organic Letters,
Год журнала:
2016,
Номер
18(15), С. 3662 - 3665
Опубликована: Июль 14, 2016
Cooperative
cobalt-
and
copper-catalyzed
C–H
activation
of
imidate
esters
oxidative
coupling
with
anthranils
allowed
efficient
synthesis
1H-indazoles
in
the
absence
metal
oxidants.
The
anthranil
acts
as
a
convenient
aminating
reagent
well
an
organic
oxidant
this
transformation.
copper
catalyst
likely
functions
at
stage
N–N
formation.
Chemistry - A European Journal,
Год журнала:
2018,
Номер
25(13), С. 3156 - 3180
Опубликована: Сен. 5, 2018
Abstract
Nitrene‐transfer
reactions
are
powerful
synthetic
tools
for
the
direct
incorporation
of
nitrogen
atoms
into
organic
molecules.
The
discovery
novel
nitrene‐transfer
has
been
dominantly
supported
not
only
by
improvements
in
transition‐metal
catalysts
but
also
employment
precursors
nitrenoids.
Since
pioneering
work
involving
use
azides
and
iminoiodinanes
as
practical
nitrogen‐containing
compounds
was
reported,
a
new
approach
using
various
N‐heterocycles
containing
strain
energy
or
weak
bond
emerged.
In
this
review,
we
briefly
summarize
history
chemistry
from
viewpoint
its
precursors.
particular,
such
2
H
‐azirines,
1,4,2‐dioxazol‐5‐ones,
1,2,4‐oxadiazol‐5‐ones,
isoxazol‐5(4
)‐ones,
isoxazoles
is
comprehensively
described,
showing
recent
remarkable
progress
chemistry.
Organic Letters,
Год журнала:
2017,
Номер
19(7), С. 1812 - 1815
Опубликована: Март 30, 2017
Cobalt(III)
and
rhodium(III)
catalysts
exhibited
complementary
scope
in
C–H
amidation
of
aryl
enaminones.
The
reactions
proceeded
with
broad
under
the
assistance
a
weakly
coordinating
bifunctional
enaminone
directing
group.
electrophilicity
group
can
be
further
utilized
subsequent
hydrolysis–cyclization
to
afford
NH
4-quinolones
telescoping
reactions.
Organic Letters,
Год журнала:
2017,
Номер
19(5), С. 1128 - 1131
Опубликована: Фев. 17, 2017
A
microwave-assisted,
Cp*CoIII-catalyzed
direct
C–H
activation/double
C–N
bond
formation
reaction
of
simple
NH-sulfoximines
with
1,4,2-dioxazol-5-ones
to
produce
diverse
thiadiazine-1-oxides
is
reported.
The
tolerates
a
broad
range
functional
groups
under
external
oxidant-free
conditions
and
only
releases
CO2
H2O
as
the
sole
byproducts.
preliminary
mechanistic
studies
revealed
an
electrophilic
metalation
pathway
likely
involved
in
reaction.
Angewandte Chemie International Edition,
Год журнала:
2017,
Номер
56(28), С. 8163 - 8167
Опубликована: Май 17, 2017
Abstract
Rhodium(III)‐
and
cobalt(III)‐catalyzed
C−H
activation
of
indoles
coupling
with
1,6‐enynes
is
discussed.
Under
rhodium(III)
catalysis,
the
alkyne
insertion
follows
2,1‐regioselectivity
a
subsequent
type‐I
intramolecular
Diels–Alder
reaction
(IMDA)
to
afford
[6,5]‐fused
cycles.
When
catalyzed
by
cobalt(III)
congener,
1,2‐insertion
preferred,
followed
rare
type‐II
IMDA,
thus
leading
bridged
[3,3,1]‐cycles.
This
selectivity
was
mainly
tuned
steric
sensitivity
catalyst.
ACS Catalysis,
Год журнала:
2016,
Номер
6(9), С. 5930 - 5934
Опубликована: Авг. 3, 2016
Air-stable
and
convenient
amidobenziodoxolones
as
an
amidating
reagent
were
disclosed
to
enable
direct
amidation
on
a
wide
range
of
C(sp2)–H
bonds
(hetero)arenes
alkenes,
well
unactivated
C(sp3)–H
under
RhIII
catalysis.
The
approach
access
49
examples
structurally
diverse
amides
is
featured
by
mild
conditions,
complete
chemoselectivity
regioselectivity,
broad
substrate
scope
(not
limited
strongly
heterocyclic
coordinating
groups),
tolerance
valuable
functional
substituents,
such
unprotected
amine
hydroxyl
groups.
synthetic
applicability
this
protocol
also
demonstrated
late-stage
functionalization
biologically
important
scaffolds.
ACS Catalysis,
Год журнала:
2017,
Номер
7(10), С. 7296 - 7304
Опубликована: Сен. 12, 2017
An
efficient,
atom-economical,
and
regioselective
insertion
of
indoles
into
terminal
alkynes
has
been
realized
via
cobalt(III)-catalyzed
C–H
activation
under
mild
conditions,
leading
to
efficient
synthesis
α-gem-vinylindoles.
The
the
follows
a
rare
1,2-selectivity,
silyl
alkynes,
alkyl
propargyl
alcohols,
protected
amines
are
all
applicable.
mechanism
this
hydroarylation
system
studied
in
detail
by
combination
experimental
computational
approaches.
In
reaction
regioselectivity
is
dictated
steric
effects
alkyne
substituent,
especially
protonolysis
stage.
However,
for
amines,
selectivity
results
from
electronic
during
step,
with
being
insignificant
determination
selectivity.
internal
also
coupled
high
efficiency
but
low
regioselectivity.
Comparisons
cobalt,
rhodium,
iridium
catalysts
have
made
terms
reactivity,
both
cobalt
catalysts.
Organic Letters,
Год журнала:
2017,
Номер
19(9), С. 2418 - 2421
Опубликована: Апрель 20, 2017
We
report
herein
the
development
of
a
Co(III)-catalyzed
enaminone-directed
C–H
amidation
method
for
synthetic
access
to
quinolones,
an
important
heterocyclic
scaffold
diverse
pharmaceutically
active
structures.
The
coupling
with
dioxazolones
and
subsequent
deacylation
installed
amide
group
allow
consecutive
C–N
generation
quinolones
wide-ranging
compatible
substituent
patterns.