Umpolung‐Enabled Divergent Dearomative Carbonylations
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(33)
Опубликована: Май 31, 2024
Although
dearomative
functionalizations
enable
the
direct
conversion
of
flat
aromatics
into
precious
three-dimensional
architectures,
case
for
simple
arenes
remains
largely
underdeveloped
owing
to
high
aromatic
stabilization
energy.
We
herein
report
a
sequential
addition
two
nucleophiles
arene
π-bonds
through
umpolung
chromium-arene
complexes.
This
mode
enables
divergent
carbonylation
reactions
benzene
derivatives
by
tolerating
various
in
combination
with
alcohols
or
amines
under
CO-gas-free
conditions,
thus
providing
modular
access
functionalized
esters
amides.
The
tunable
synthesis
1,3-
1,4-cyclohexadienes
as
well
construction
carbon
quaternary
centers
further
highlight
versatility
this
dearomatization.
Diverse
late-stage
modifications
and
derivatizations
towards
synthetically
challenging
bioactive
molecules
reveal
synthetic
utility.
A
possible
mechanism
was
proposed
based
on
control
experiments
intermediate
tracking.
Язык: Английский
Dearomative 1,2‐(Deutero)Hydrotrifluoromethylation of Chromium‐Bound Arenes
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(20), С. 4199 - 4204
Опубликована: Июль 19, 2024
Abstract
Dearomative
trifluoromethylation
of
arenes
provides
an
ideal
method
for
constructing
CF
3
‐containing
three‐dimensional
architectures
which
are
increasing
interest
in
drug
discovery.
However,
such
transformation
is
rare
and
challenging
because
the
inherently
low
reactivity
arene
π‐systems
selectivity
issues.
Herein,
we
disclose
a
general
dearomative
1,2‐hydrotrifluoromethylation
(hetero)arenes
utilizing
activation
by
temporary
π‐complexation
to
chromium,
thus
affording
convenient
access
1,3‐cyclohexadienes
bearing
privileged
group.
The
versatility
this
strategy
further
enables
1,2‐deuterotrifluoromethylation
with
high
deuterated
ratios.
related
1,2‐(deutero)hydroperfluoroethylation
reactions
were
conducted
well
range
chromium‐bound
(hetero)arenes.
Finally,
reasonable
mechanism
was
proposed
based
on
intermediate
capture
control
experiments.
Язык: Английский
Umpolung‐Enabled Divergent Dearomative Carbonylations
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 31, 2024
Abstract
Although
dearomative
functionalizations
enable
the
direct
conversion
of
flat
aromatics
into
precious
three‐dimensional
architectures,
case
for
simple
arenes
remains
largely
underdeveloped
owing
to
high
aromatic
stabilization
energy.
We
herein
report
a
sequential
addition
two
nucleophiles
arene
π‐bonds
through
umpolung
chromium–arene
complexes.
This
mode
enables
divergent
carbonylation
reactions
benzene
derivatives
by
tolerating
various
in
combination
with
alcohols
or
amines
under
CO‐gas‐free
conditions,
thus
providing
modular
access
functionalized
esters
amides.
The
tunable
synthesis
1,3‐
1,4‐cyclohexadienes
as
well
construction
carbon
quaternary
centers
further
highlight
versatility
this
dearomatization.
Diverse
late‐stage
modifications
and
derivatizations
towards
synthetically
challenging
bioactive
molecules
reveal
synthetic
utility.
A
possible
mechanism
was
proposed
based
on
control
experiments
intermediate
tracking.
Язык: Английский
Chromium‐Mediated Dearomative Allylic Addition to Arenes
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(46)
Опубликована: Авг. 23, 2024
Abstract
In
comparison
with
the
well‐established
allylic
additions
to
C=O,
C=N,
and
C=C
double
bonds,
dearomative
addition
arene
π‐systems
is
heavily
underdeveloped
due
severe
challenge
in
breaking
aromatic
resonance
stabilization.
Herein,
we
disclose
a
general
efficient
chromium‐bound
arenes
using
allylsilanes
as
pronucleophiles,
thus
affording
convenient
access
allyl‐functionalized
1,3‐cyclohexadiene
building
blocks.
With
commercially
available
deuterium
sources,
versatility
of
this
strategy
further
enables
an
1,2‐deuteroallylation
high
level
incorporation.
Finally,
preliminary
try
on
asymmetric
hydroallylation
based
chiral
auxiliary
described.
Язык: Английский