Organic Letters,
Год журнала:
2023,
Номер
25(19), С. 3543 - 3547
Опубликована: Май 9, 2023
A
direct
dearomative
[4
+
2]
annulation
of
electron-poor
N-heteroarenes
with
azoalkenes
generated
in
situ
from
α-halogeno
hydrazones
was
developed
under
mild
conditions.
Accordingly,
a
series
fused
polycyclic
tetrahydro-1,2,4-triazines
potential
biological
activity
were
obtained
up
to
96%
yield.
Various
and
N-heteroarenes,
such
as
pyridines,
quinolines,
isoquinolines,
phenanthridine,
benzothiazole,
tolerated
by
this
reaction.
The
general
applicability
method
shown
upscale
synthesis
product
derivatization.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1596 - 1606
Опубликована: Янв. 14, 2025
Transition
metal-catalyzed
reductive
coupling
chemistry
has
been
recognized
as
a
powerful
tool
for
the
synthesis
of
diverse
organic
molecules.
However,
despite
enormous
progress
in
this
field,
there
is
no
precedent
tandem
widely
accessible
nitriles
with
electrophiles
that
contain
σ-
and
π-type
(σ/π-type)
electrophilic
functional
groups
simultaneously.
Herein,
we
have
established
unique
cobalt
catalysis
system,
enabling
chemoselective
coupling/tandem
cyclization
reaction
aryl
halides
(Br,
Cl,
I)
bearing
carbonyl
moiety
variety
aryl,
alkenyl,
alkyl
via
carbocobaltation
unknown
yet.
The
protocol
allows
modular
structurally
isoquinolines
wide
substrate
scope
(>60
examples),
good
functionalities
tolerance,
chemoselectivity.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(6)
Опубликована: Дек. 1, 2022
Dearomatization
reactions
involving
radical
cyclizations
can
facilitate
the
synthesis
of
complex
polycyclic
systems
that
find
applications
in
medicinal
chemistry
and
natural
product
synthesis.
Here
we
employ
redox-neutral
photocatalysis
to
affect
a
spirocyclization
transforms
biaryls
into
spirocyclic
cyclohexadienones
under
mild
reaction
conditions.
In
departure
from
previously
reported
methods,
our
work
demonstrates
polarity
mismatched
addition
nucleophilic
an
electron
rich
arene,
allows
regioselective
2,4-
or
2,5-cyclohexadienones
with
broad
functional
group
tolerance.
By
transforming
spirocycles,
methodology
accesses
underexplored
three-dimensional
chemical
space,
provides
efficient
means
creating
quaternary
spirocenters
apply
first
cytotoxic
plant
metabolite
denobilone
A.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(3), С. 270 - 294
Опубликована: Янв. 10, 2023
Abstract
Dearomatization
reactions
are
among
the
most
efficient
chemical
processes,
combining
atom
economy,
stereospecificity
and
ability
to
generate
molecular
complexity
in
a
single
step.
Dearomative
vinylation
provide
synthetic
connection
between
readily
available,
simple
aromatic
starting
materials
more
unsaturated
alkynes.
The
last
decade
has
witnessed
steady
increase
development
of
transition
metal‐catalyzed
dearomative
methods
electron
rich
compounds
with
alkynes,
providing
new
approaches
high‐value
building
blocks
natural
products.
This
review
aims
serve
as
comprehensive
reference
for
work
magnified
image
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3165 - 3172
Опубликована: Янв. 1, 2024
Amine-tethered
spiro-cyclic
skeletons
were
obtained
through
photo-induced
100%-atom-economic
dearomatization,
involving
the
cleavage
of
α-C(sp
3
)–H
amines.
Pentacyclic
framework
was
achieved
from
pyridinyl
ring
within
two
steps.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 13, 2025
A
Tf2O-triggered
dearomative
triazinylmethylation
of
isoquinolines
and
other
azaarenes
utilizing
acetonitrile
as
the
nucleophile
has
been
developed
through
a
formal
five-component
reaction.
This
method
showcases
broad
substrate
scope
exceptional
functional
group
compatibility,
presenting
mild
expedient
synthetic
approach.
Kinetic
studies,
including
kinetic
isotope
effect
(KIE)
Hammett
analysis,
indicate
that
activation
by
Tf2O
constitutes
rate-limiting
step.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
divergent
denitrogenation/recyclization
of
1,2,3,4-benzothiatriazine-1,1-dioxides
is
disclosed,
including
C(sp
2
)-alkyl
transposition
and
aniline
dearomatization.
Chemical Communications,
Год журнала:
2023,
Номер
59(30), С. 4405 - 4422
Опубликована: Янв. 1, 2023
Alkynes
as
unsaturated
hydrocarbons
have
long
been
used
for
cyclization
reactions.
Various
transition
metal-catalyzed
cyclizations
of
alkynes
reported
in
the
past
decades.
In
this
minireview,
we
mainly
summarize
recent
asymmetric
with
other
functional
groups
such
carbonyl-alkynes,
cyano-alkynes,
and
enynes
under
catalytic
system
nickel
chiral
ligands.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(7)
Опубликована: Янв. 2, 2024
Abstract
Chromium‐catalyzed
enantioselective
Nozaki–Hiyama–Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon‐heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt‐catalyzed
aza‐NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α‐vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Green Synthesis and Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Фев. 1, 2024
1,7-Hydride
transfer-involved
dearomatization
of
quinolines
toward
C3-spiro
hydroquinoline
derivatives
has
been
developed.
This
method
offers
a
protocol
to
achieve
the
electron-deficient
arenes
via
redox-neutral
hydride
transfer
process.
A
series
hydroquinolines
can
be
provided
in
moderate
excellent
yields
(up
98%)
with
good
diastereoselectivities.
Significant
advantages
such
as
high
step-
and
atom-economy,
well
mild
conditions,
make
it
an
appealing
alternative
quinolines.
