Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 27, 2025
A
dearomative
strategy
to
regioselectively
modify
arenes
using
a
"diene"
synthon
within
aromatic
rings
provides
access
highly
functionalized
heterocycles
from
abundant
feedstocks
and
represents
an
alternative
synthetic
approach
besides
traditional
cross-coupling
C-H
functionalization
methodologies.
In
this
study,
we
present
efficient
method
for
selectively
introducing
boron
onto
quinolines
through
hydroboration
easily
accessible
stable
phosphine-ligated
borane
complexes.
The
vicinal
5,6-
conjugate
5,8-hydroborated
products
could
be
obtained
by
modifying
the
phosphine
ligand.
Drawing
inspiration
diverse
organoboron
transformations,
these
building
blocks
were
diversified
range
of
downstream
functionalizations,
providing
modular
pathways
skeletal
modifications
variety
challenging
heterocycles.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2789 - 2797
Опубликована: Янв. 18, 2024
Dearomative
photocycloaddition
of
monocyclic
arenes
is
an
appealing
strategy
for
comprehending
the
concept
"escape
from
flatland".
This
brings
replacement
readily
available
planar
aromatic
hydrocarbon
units
with
a
3D
fused
bicyclic
core
sp3-enriched
carbon
units.
Herein,
we
outline
intermolecular
approach
dearomative
phenols.
In
order
to
circumvent
ground-state
aromaticity
and
construct
conformationally
restrained
building
blocks,
bicyclo[1.1.0]butanes
were
chosen
as
coupling
partners.
renders
straightforward
access
bicyclo[2.1.1]hexane
unit
cyclic
enone
moiety,
which
further
contributed
synthetic
linchpin
postmodifications.
Mechanistic
experiment
advocates
plausible
onset
both
reactants,
depending
on
redox
potential.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 2939 - 2943
Опубликована: Янв. 12, 2024
A
practical
method
for
the
synthesis
of
15N-labeled
azines
with
a
high
degree
isotopic
enrichment
is
described.
Activation
azine
heterocycles
an
electron-deficient
arene
allows
facile
substitution
nitrogen
atom
specifically
designed
reagent
that
undergoes
canonical
ANRORC-type
mechanism.
wide
range
can
be
converted
to
their
corresponding
15N
isotopologs
using
this
method,
and
it
also
dearomative
access
reduced
heterocyclic
congeners.
short
formal
15N-solifenacin
accomplished
as
well
demonstrate
application
generating
labeled
pharmaceuticals.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(12)
Опубликована: Янв. 27, 2023
Abstract
Dearomative
cycloadditions
are
a
powerful
tool
to
access
large
chemical
space
exploiting
simple
and
ubiquitous
building
blocks.
The
energetic
burden
due
the
loss
of
aromaticity
has
however
greatly
limited
their
synthetic
potential.
We
devised
general
intramolecular
method
that
overcomes
these
limitations
thanks
photosensitization
allenamides.
visible‐light‐promoted
process
gives
complex
[2.2.2]‐(hetero)‐bicyclooctadienes
at
room
temperature,
likely
through
stabilization
transient
(bi)radicals
by
naphthalene.
reaction
tolerates
several
valuable
functionalities,
offering
convenient
handle
for
myriad
applications,
including
original
isoindoles
metal
complexes.
Natural Product Reports,
Год журнала:
2023,
Номер
41(2), С. 208 - 227
Опубликована: Июнь 9, 2023
Covering:
2008
to
2023This
review
will
describe
oxidative
phenol
coupling
as
applied
in
the
total
synthesis
of
natural
products.
This
covers
catalytic
and
electrochemical
methods
with
a
brief
comparison
stoichiometric
enzymatic
systems
assessing
their
practicality,
atom
economy,
other
measures.
Natural
products
forged
by
C-C
C-O
couplings
well
from
alkenyl
be
addressed.
Additionally,
exploration
into
phenols
related
species
(carbazoles,
indoles,
aryl
ethers,
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(21)
Опубликована: Март 14, 2024
Abstract
Dearomative
partial
reduction
is
an
extraordinary
approach
for
transforming
benzenoid
arenes
and
has
been
well‐known
many
decades,
as
exemplified
by
the
dehydrogenation
of
Birch
hydroarylation
Crich
addition.
Despite
its
remarkable
importance
in
synthesis,
this
field
experienced
slow
progress
over
last
half‐century.
However,
a
revival
observed
with
recent
introduction
electrochemical
photochemical
methods.
In
Minireview,
we
summarize
advancements
dearomative
arenes,
including
dihydrogenation,
hydroalkylation,
arylation,
alkenylation,
amination,
borylation
others.
Further,
intriguing
utilization
synthesis
natural
products
also
emphasized.
It
anticipated
that
Minireview
will
stimulate
further
arene
transformations.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16982 - 16989
Опубликована: Июнь 13, 2024
Catalytic
asymmetric
dearomatization
(CADA)
reactions
have
evolved
into
an
efficient
strategy
for
accessing
chiral
polycyclic
and
spirocyclic
scaffolds
from
readily
available
planar
aromatics.
Despite
the
significant
developments,
CADA
reaction
of
naphthalenes
remains
underdeveloped.
Herein,
we
report
a
Gd(III)-catalyzed
naphthalene
with
PyBox
ligand
via
visible-light-enabled
[4
+
2]
cycloaddition.
This
features
application
Gd/PyBox
complex,
which
regulates
reactivity
selectivity
simultaneously,
in
excited-state
catalysis.
A
wide
range
functional
groups
is
compatible
this
protocol,
giving
highly
enantioenriched
bridged
polycycles
excellent
yields
(up
to
96%)
>20:1
chemoselectivity,
dr,
>99%
ee).
The
synthetic
utility
demonstrated
by
2
mmol
scale
reaction,
removal
directing
group,
diversifications
products.
Preliminary
mechanistic
experiments
are
performed
elucidate
mechanism.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 19, 2024
Abstract
Medium-sized-ring
compounds
have
been
recognized
as
challenging
synthetic
targets
in
organic
chemistry.
Especially,
the
difficulty
of
synthesis
will
be
augmented
if
an
E
-olefin
moiety
is
embedded.
Recently,
photo-induced
dearomative
cycloaddition
reactions
that
proceed
via
energy
transfer
mechanism
witnessed
significant
developments
and
provided
powerful
methods
for
transformations
are
not
easily
realized
under
thermal
conditions.
Herein,
we
report
intramolecular
[5
+
4]
naphthalene-derived
vinylcyclopropanes
visible-light
irradiation
a
proper
triplet
photosensitizer.
The
reaction
affords
dearomatized
polycyclic
molecules
possessing
nine-membered-ring
with
good
yields
(up
to
86%)
stereoselectivity
8.8/1
/
Z
).
Detailed
computational
studies
reveal
origin
behind
favorable
formation
thermodynamically
less
stable
isomers.
Diverse
derivations
products
also
demonstrated.