Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(24), P. 5151 - 5159
Published: Aug. 29, 2024
Abstract
A
copper
or
silver‐catalyzed
cascade
addition/5‐
exo‐dig
cyclization/isomerization
reaction
of
isothiocyanate
with
ynone
has
been
developed.
This
strategy
enables
the
synthesis
a
variety
(
Z
)‐2‐ylidene‐5‐aminothiophen‐3‐one
derivatives
diverse
substitutions
in
single
vessel.
The
method
is
featured
pot‐economy
as
well
regio‐
and
‐selectivity.
Several
biologically
active
molecules
could
be
modified
using
this
strategy.
Moreover,
relevant
indole‐fused
indole‐substituted
thiophenone
were
also
assembled
one
pot
by
merging
other
bond
formation
methods.
Based
on
experiments
related
reports,
pathway
triggered
addition
ynone‐derived
radical
towards
C(
sp
)‐atom
was
proposed
to
elucidate
probable
process
transformation.
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 Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(22), P. 6311 - 6318
Published: Jan. 1, 2024
Co-catalyzed
asymmetric
reductive
addition
of
ketimine
with
cyclopropyl
chloride
has
been
realized
to
access
diverse
chiral
amino
esters
bearing
fragments
broad
functional
group
tolerance
and
excellent
enantioselectivities.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(24), P. 5151 - 5159
Published: Aug. 29, 2024
Abstract
A
copper
or
silver‐catalyzed
cascade
addition/5‐
exo‐dig
cyclization/isomerization
reaction
of
isothiocyanate
with
ynone
has
been
developed.
This
strategy
enables
the
synthesis
a
variety
(
Z
)‐2‐ylidene‐5‐aminothiophen‐3‐one
derivatives
diverse
substitutions
in
single
vessel.
The
method
is
featured
pot‐economy
as
well
regio‐
and
‐selectivity.
Several
biologically
active
molecules
could
be
modified
using
this
strategy.
Moreover,
relevant
indole‐fused
indole‐substituted
thiophenone
were
also
assembled
one
pot
by
merging
other
bond
formation
methods.
Based
on
experiments
related
reports,
pathway
triggered
addition
ynone‐derived
radical
towards
C(
sp
)‐atom
was
proposed
to
elucidate
probable
process
transformation.
