Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(19), P. 3543 - 3547
Published: May 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.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2359 - 2364
Published: March 15, 2024
A
palladium-catalyzed
dearomative
diarylation
of
C2-deuterated
or
C2-nonsubstituted
indoles
through
domino
Heck/Suzuki
coupling
is
established.
Relying
on
electron-deficient
phosphite
ligand,
side
reactions
including
intermolecular
Suzuki
and
intramolecular
C–D/H
arylation
are
inhibited
a
wide
range
2,3-diarylated
indolines
bearing
vicinal
tertiary
stereocenters
deuterated
ones
afforded
in
moderate
to
excellent
yields
(up
94%)
diastereoselectivities
(>20:1).
The
catalyst
loading
can
be
lowered
0.02
mol
%
at
elevated
temperature.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 8294 - 8309
Published: May 13, 2024
In
synthetic
organic
chemistry,
unconventional
strategies
for
advanced
chemical
synthesis
pose
interesting
and
challenging
problems.
Alcohols
act
as
alkylating
agents
in
the
C–C
C–N
bond-forming
reactions
via
dehydrogenative
borrowing
hydrogen
strategy
traditional
transition
metal
catalysis;
however,
an
acylating
agent
is
rarely
reported.
Here,
we
report
coupling
of
benzylic
alcohols
with
internal
alkynes
under
nickel(II)
catalysis,
wherein
alcohol
used
agent.
This
reaction
system
affords
a
wide
range
α-branched
aryl
ketone
derivatives
zero
waste
generation
through
umpolung
strategy.
Moreover,
have
demonstrated
chemodivergent
applications
α-disubstituted
ketones
to
other
valuable
building
blocks,
including
large-scale
β-deuterated
branched
ketones.
Several
spectroscopic
studies,
intermediate
identification,
density
functional
theory
calculations
were
performed
elucidate
mechanism.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 3, 2024
The
Barbier
reaction
is
a
reductive-type
addition
of
an
aldehyde
or
ketone
with
organic
electrophile
in
the
presence
terminal
metal
reductant,
providing
straightforward
and
efficient
method
for
carbon-carbon
bond
formation.
This
possesses
advantage
circumventing
preparation
moisture-
air-sensitive
organometallic
reagents.
However,
catalytic
ketones
to
construct
tetrasubstituted
stereogenic
centers
largely
underdeveloped,
despite
its
great
potential
accessing
synthetically
challenging
chiral
tertiary
alcohol.
Particularly,
leveraging
unactivated
alkyl
electrophiles
as
coupling
components
still
rarely
exploited.
Herein,
we
disclose
photoredox-assisted
cobalt-catalyzed
asymmetric
alkylative
Barbier-type
address
aforementioned
challenges,
thereby
allowing
construction
highly
congested
carbon
centers.
fragments
could
be
either
readily
accessible
halides
redox-active
esters
generated
through
decarboxylative
pathway.
Both
types
include
primary,
secondary,
ones,
thus
affording
diverse
enantioenriched
alcohols
broad
substrate
scope.
enantioselective
protocol
applied
expedient
synthesis
core
structure
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(19), P. 3543 - 3547
Published: May 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.
