Abstract
Traditional
palladium‐catalyzed
dearomatization
of
(hetero)arenes
takes
place
via
an
ionic
pathway
and
usually
requires
elevated
temperatures
to
overcome
the
energy
barrier
dearomative
insertion
step.
Herein,
a
combination
radical
two‐electron
pathways
is
disclosed,
which
enables
room
temperature
3D
transformations
nonactivated
phenyl
rings
with
Pd(0)
as
catalyst.
Experimental
results
together
density
functional
theory
(DFT)
calculations
indicate
versatile
π‐allyl
Pd(II)
species,
cyclohexadienyl
Pd(II),
possibly
involved
in
dearomatization.
This
species
generated
by
combining
Pd(I).
The
provides
chemoselective
(carboamination
trieneylation),
regioselective
(1,2‐carboamination),
diastereoselective
(carbonyl‐group
directed
face
selectivity)
conversions.
Organic Letters,
Год журнала:
2022,
Номер
24(3), С. 966 - 970
Опубликована: Янв. 19, 2022
A
novel
Brønsted-acid-promoted
selective
C2-N1
ring-expansion
reaction
of
indoles
has
been
developed
that
provides
a
rapid
and
efficient
protocol
for
the
preparation
fused
quinolines.
variety
corresponding
quinolines
were
obtained
in
high
yields.
Controlled
experiments
revealed
C2-spiroindolenines
might
be
intermediates
this
reaction.
The
notable
advantages
process
include
excellent
yields,
good
functional
group
tolerance,
operational
simplicity.
Chemical Communications,
Год журнала:
2022,
Номер
58(39), С. 5893 - 5896
Опубликована: Янв. 1, 2022
A
NiH-catalyzed
intermolecular
dearomative
hydroalkylation
of
indoles
has
been
developed,
which
assembles
an
array
structurally
diverse
C2-alkylated
indolines
with
moderate
to
excellent
yields.
This
protocol
exhibits
good
functional
group
tolerance,
allowing
for
late-stage
functionalization
complex
drug
molecules.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(30)
Опубликована: Май 16, 2022
The
direct
dearomative
addition
of
arenes
to
the
C3
position
unprotected
indoles
is
reported
under
operationally
simple
conditions,
using
triflic
acid
at
room
temperature.
present
regioselective
hydroarylation
a
straightforward
manner
generate
an
electrophilic
indole
from
unbiased
in
sharp
contrast
previous
strategies.
This
atom-economical
method
delivers
biologically
relevant
3-arylindolines
and
3,3-spiroindolines
high
yields
regioselectivities
both
intra-
intermolecular
processes.
DFT
computations
suggest
stabilization
cationic
or
dicationic
intermediates
with
H-bonded
(TfOH)
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 6237 - 6246
Опубликована: Апрель 11, 2023
Benzocyclic
boronates
have
attracted
increasing
research
interest
in
drug
chemistry
and
organic
synthesis
recent
years.
Herein,
we
report
a
facile
access
to
benzocyclic
through
photopromoted
intramolecular
arylborylation
of
allyl
aryldiazonium
salts.
This
simple
protocol
features
broad
scope,
allowing
the
formation
variously
functionalized
borates
bearing
dihydrobenzofuran,
dihydroindene,
benzothiophene,
indoline
skeletons
under
mild
sustainable
conditions.
Abstract
Traditional
palladium‐catalyzed
dearomatization
of
(hetero)arenes
takes
place
via
an
ionic
pathway
and
usually
requires
elevated
temperatures
to
overcome
the
energy
barrier
dearomative
insertion
step.
Herein,
a
combination
radical
two‐electron
pathways
is
disclosed,
which
enables
room
temperature
3D
transformations
nonactivated
phenyl
rings
with
Pd(0)
as
catalyst.
Experimental
results
together
density
functional
theory
(DFT)
calculations
indicate
versatile
π‐allyl
Pd(II)
species,
cyclohexadienyl
Pd(II),
possibly
involved
in
dearomatization.
This
species
generated
by
combining
Pd(I).
The
provides
chemoselective
(carboamination
trieneylation),
regioselective
(1,2‐carboamination),
diastereoselective
(carbonyl‐group
directed
face
selectivity)
conversions.
