ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(16), P. 11001 - 11011
Published: Aug. 4, 2023
The
radical
1,2-difunctionalization
reaction
of
alkynes
has
evolved
into
a
versatile
approach
to
multisubstituted
alkylenes.
However,
robust
catalytic
strategies
perform
carboamination
are
lacking,
despite
the
ubiquity
resulting
enamines
in
natural
molecules,
bioactive
and
pharmaceutical
compounds.
Herein,
we
show
that
bidentate
coordinating
group
judiciously
installed
on
amines
could
act
as
an
efficient
tool
for
enabling
trifluoromethylamidation
alkynes.
This
strategy
exhibits
broad
substrate
scope
with
good
functional
compatibility
is
amenable
late-stage
functionalization
compounds
biologically
relevant
motifs,
allowing
straightforward
synthesis
large
library
CF3-containing
enamides,
high-value
pharmacophores,
single
step
from
readily
accessible
amides,
Langlois'
reagent,
current
methodology
can
also
be
successfully
extended
difluoromethylamidation
Additionally,
various
mechanistic
experiments,
such
competition
H/D
isotopic
exchanging
trap
Hammett
studies,
kinetic
have
been
performed
better
understanding
mechanism.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(19), P. 7434 - 7438
Published: Sept. 15, 2021
We
present
a
strategy
for
the
synthesis
of
spirocyclic
cyclobutanes
with
modulable
exit
vectors
based
on
regioselective
monoborylation
spirocyclobutenes.
Using
an
inexpensive
copper
salt
and
commercially
available
bidentate
phosphine,
broad
variety
borylated
spirocycles
have
been
prepared
complete
regiocontrol.
The
boryl
moiety
provides
synthetic
handled
further
functionalization,
allowing
access
to
wide
array
building
blocks
from
common
intermediate.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(43), P. 6584 - 6587
Published: Jan. 1, 2023
We
synthesized
tetrasubstituted
olefins
regioselectively
and
stereoselectively
from
ynamides
internal
alkynes
with
sulfonyl
iodides
under
blue
LEDs
in
few
minutes.
The
key
features
are
being
metal-free,
easy
to
handle,
simple,
broad
scope,
environmentally
friendly.
Furthermore,
a
gram-scale
experiment
was
conducted,
the
corresponding
sulfonyl-iodinated
products
were
smoothly
altered
into
various
other
products.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(34), P. 18722 - 18730
Published: Aug. 15, 2023
Selective
transformation
of
alkyne
triple
bonds
to
double
serves
as
an
efficient
platform
construct
substituted
alkenes.
While
significant
advances
have
been
made
in
its
spatiotemporal
regulation,
achieving
a
multicomponent
enantioselective
reaction
that
requires
multifaceted
selectivity
issues
be
overcome
is
still
uncommon.
Here,
we
report
unprecedented
asymmetric
anti-stereoselective
borylcarbofunctionalization
terminal
alkynes
by
nickel
catalysis.
The
utilization
inexpensive
chiral
diamine
ligand
enables
the
three-component
cross-coupling
alkynes,
diboron
reagent,
and
prochiral
alkyl
electrophiles
with
high
levels
regio-,
stereo-,
enantioselectivities.
This
provides
protocol
access
enantioenriched
alkenyl
esters
bearing
α-stereogenic
center,
remarkably
practical,
has
broad
scope
outstanding
functional
group
compatibility.
In
addition,
value
this
method
highlighted
diversity
follow-up
stereoretentive
derivatizations
stereoselective
concise
synthesis
complex
drug
molecules.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(20), P. 13540 - 13560
Published: Oct. 6, 2023
Bidentate
P,N
ligands,
integrating
phosphine
and
nitrogen
donors,
are
highlighted
for
their
versatile
characteristics,
offering
both
electronic
steric
tunability.
Their
hemilabile
nature,
coupled
with
the
ability
to
modulate
properties
through
choice
of
donor
atoms
substituents,
has
expanded
horizons
chemical
transformations.
This
Review
focuses
on
Ni-catalyzed
cross-coupling
reactions
mediated
by
ligands.
The
asymmetrical
nature
each
atom
playing
a
specific
role
in
catalytic
cycle,
offers
control,
stability,
unique
regioselectivity
processes.
In
particular,
Ni/P,N-catalytic
system
exhibits
remarkable
reactivity
π-substrates
including
alkenes,
alkynes,
allenes.
A
thorough
mechanistic
understanding
these
processes
insights
into
trends
future
directions
Ni/P,N-catalyzed
reactions.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(16), P. 11001 - 11011
Published: Aug. 4, 2023
The
radical
1,2-difunctionalization
reaction
of
alkynes
has
evolved
into
a
versatile
approach
to
multisubstituted
alkylenes.
However,
robust
catalytic
strategies
perform
carboamination
are
lacking,
despite
the
ubiquity
resulting
enamines
in
natural
molecules,
bioactive
and
pharmaceutical
compounds.
Herein,
we
show
that
bidentate
coordinating
group
judiciously
installed
on
amines
could
act
as
an
efficient
tool
for
enabling
trifluoromethylamidation
alkynes.
This
strategy
exhibits
broad
substrate
scope
with
good
functional
compatibility
is
amenable
late-stage
functionalization
compounds
biologically
relevant
motifs,
allowing
straightforward
synthesis
large
library
CF3-containing
enamides,
high-value
pharmacophores,
single
step
from
readily
accessible
amides,
Langlois'
reagent,
current
methodology
can
also
be
successfully
extended
difluoromethylamidation
Additionally,
various
mechanistic
experiments,
such
competition
H/D
isotopic
exchanging
trap
Hammett
studies,
kinetic
have
been
performed
better
understanding
mechanism.
