A
simple
copper(I)/N-heterocyclic
carbene
complex
facilitates
a
H2-mediated
C–C
coupling
reaction
of
internal
alkynes
and
allylic
chlorides.
The
catalytic
protocol
delivers
the
corresponding
1,4-dienes
(skipped
dienes)
with
high
chemo-,
regio-
stereoselectivity
without
any
isomerization
to
thermodynamically
more
stable
1,3-dienes
or
overreduction
corre-sponding
alkanes.
allows
for
exploitation
“copper
hydride
catalysis”
H2
as
terminal
reducing
agent
source
hydrides
forging
new
bonds.
In
this
way,
approach
gives
rise
bond
forming
reactions
3d
metal
need
stoichiometric
organometallic
agent.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 10167 - 10176
Published: March 27, 2024
The
π-bond
enrichment
frameworks
not
only
serve
as
a
crucial
building
block
in
organic
synthesis
but
also
assume
pivotal
role
the
fields
of
materials
science,
biomedicine,
photochemistry,
and
other
related
disciplines
owing
to
their
distinctive
structural
characteristics.
incorporation
various
substituents
into
C═C
double
bonds
tetrasubstituted
alkenes
is
currently
highly
significant
research
area.
However,
with
diverse
on
poses
challenge
achieving
stereoselectivity.
Here,
we
reported
an
efficient
convergent
route
Cu-catalyzed
borylalkynylation
both
symmetrical
unsymmetrical
1,3-diynes,
B2pin2,
acetylene
bromide
construction
boronated
phenyldiethynylethylene
(BPDEE)
derivatives
excellent
chemo-,
stereo-,
regioselectivities.
BPDEE
could
transform
novel
π-conjugated
gem-diphenyldiethynylethylene
(DPDEE),
vinylphenyldiethynylethylene
(VPDEE),
phenyltriethynylethylene
(PTEE)
by
stepwise
process,
which
provides
flexible
platform
for
complex
that
were
difficult
synthesize
previous
methods.
initial
optical
characterization
revealed
synthesized
molecules
exhibited
aggregation-induced
emission
(AIE)
properties,
further
establishes
groundwork
future
applications
enriches
advances
field
functional
research.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(15), P. 11318 - 11331
Published: July 15, 2024
Catalytic
enantioselective
borylation
reactions
of
unsaturated
bonds
as
powerful
tools
for
the
synthesis
diverse
chiral
organoboron
compounds
have
gained
much
attention
and
wide
applications
in
various
fields.
However,
atroposelective
arylboration
reaction
with
carbon–carbon
triple
1,3-enynes
to
obtain
axially
1,3-dienylboronates
remains
an
elusive
significant
challenge.
Hence,
we
develop
a
cooperative
copper-
palladium-catalyzed
assemble
plentiful
function
enriched
single
step
from
easily
available
1,3-enynes,
B2pin2,
aryl
bromides
high
levels
chemo-,
regio-,
stereo-,
atroposelectivity.
The
mild
conditions
lead
good
functional
group
tolerance,
which
is
proven
by
broad
substrate
scope
late-stage
functionalizations
bioactive
or
drug
molecules.
Moreover,
can
be
scaled
up,
series
further
transformations
achieved.
It
worth
emphasizing
that
several
olefin
catalysts
ligands
axial
chirality
also
synthesized
through
corresponding
elaborations
such
products,
explains
transformative
ability
application
potential
1,3-dienylboronates.
mechanism
experiment
density
theory
(DFT)
calculations
revealed
process
copper
palladium
catalysis,
indicating
chemoselectivity
regioselectivity
boration
are
determined
enyne
insertion
on
copper,
atroposelectivity
controlled
reductive
elimination
center.
Meanwhile,
calculation
demonstrated
distinct
interactions
between
P═O
C═O
groups
Pd
Bpin
center
key
transition
state
formation
products
varying
configurations
while
employing
identical
configuration
ligands.
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.
Israel Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
63(7-8)
Published: March 9, 2023
Abstract
Classical
hydroboration
is
the
textbook
example
of
an
organometallic
reaction
under
rigorous
frontier
orbital
control:
a
synergetic
bonding
mode
between
substrate
and
reagent
evolves
into
four‐membered
transition
state
that
enforces
syn
/suprafacial
delivery
H−BR
2
to
π‐system.
This
strict
stereochemical
“law”
remained
valid
for
decades,
even
after
advent
metal‐catalyzed
hydroboration.
During
last
decade,
however,
numerous
possibilities
emerged
allow
this
paradigm
be
challenged.
Thus,
direct
trans
‐hydroboration
terminal
as
well
internal
alkynes
was
achieved
through
radical,
ionic,
organocatalytic,
manifolds,
which
are
summarized
in
review.
Among
them,
pathways
involving
either
metal
vinylidenes
(Rh,
Ir,
Ru,
Fe)
derived
from
or
metallacyclopropenes
(η
‐vinylmetal
complexes)
triple
bond
[Cp
X
Ru]‐based
catalyst
represent
currently
most
widely
applicable
solutions.
The
latter
type
intermediates
also
accountable
equally
perplexing
gem
alkynes:
geminal
borane
has
no
precedent
classical
canon.
only
forerunner
‐hydrogenation,
represents
unconventional
yet
highly
useful
entry
discrete
ruthenium
carbene
complexes.
close
mechanistic
ties
these
transformations
outlined,
brief
reference
made
remotely
related
reactions
such
‐diboration
‐carboboration.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(6), P. 2236 - 2242
Published: Jan. 1, 2024
With
the
aid
of
directing
group
strategy,
an
approach
for
synthesis
alkenyl
and
1-naphthyl
boronates
with
stereo-
regioselectivity
via
ligand-controlled
Ni-catalyzed
trans
-hydroboration/carboboration
internal
alkynes
was
developed.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 25, 2025
Abstract
Stereocontrolled
construction
of
tetrasubstituted
olefins
has
been
an
attractive
issue
yet
remains
challenging
for
synthetic
chemists.
In
this
manuscript,
alkynyl
selenides,
when
treated
with
ArBCl
2
,
are
subject
to
exclusive
1,1-carboboration,
affording
alkenes
excellent
levels
E
-selectivity.
Detailed
mechanistic
studies,
supported
by
DFT
calculations,
elucidates
the
role
selenium
in
1,1-addition
process.
Coupled
subsequent
C-B
and
C-Se
bond
transformations,
protocol
constitutes
a
modular
access
stereodefined
all-carbon
alkenes.
The
merit
approach
is
demonstrated
programmed
assembly
diverse
functionalized
multi-arylated
alkenes,
especially
enabling
stereospecific
synthesis
all
six
possible
stereoisomers
tetraarylethene
(TAE)
derived
from
random
permutation
four
distinct
aryl
substituents
around
double
bond.
diversity-oriented
further
utilized
explore
different
TAE
luminogenic
properties
potential
Se-containing
antitumor
lead
compounds.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 29, 2025
We
have
developed
a
base-mediated
1,2-carboboration
of
commercially
accessible
alkynes
for
the
construction
regio-
and
stereodefined
alkenylboronates.
This
unprecedented
reaction
is
enabled
by
sodium
ethoxide
(NaOEt)
as
base
alkyl
halide
an
electrophile,
with
B2pin2
under
mild
conditions.
The
protocol
simple,
clean,
more
economical
compared
to
reported
transition
metal-catalyzed
systems.
highlights
this
methodology
include
readily
available
precursors,
broad
substrate
scope
functional
group
compatibility,
gram
scale
synthesis,
late-stage
functionalization
also
applicable
carboboration
alkenes.
Experimental
results
density
theory
(DFT)
calculations
provide
insights
into
mechanism.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(19), P. 12634 - 12642
Published: Sept. 13, 2023
A
simple
copper(I)-N-heterocyclic
carbene
complex
facilitates
a
H2-mediated
C–C
coupling
reaction
of
internal
alkynes
and
allylic
chlorides.
The
catalytic
protocol
delivers
the
corresponding
1,4-dienes
(skipped
dienes)
with
high
chemo-,
regio-,
stereoselectivity
without
any
isomerization
to
thermodynamically
more
stable
1,3-dienes
or
over-reduction
alkanes.
allows
for
exploitation
"copper
hydride
catalysis"
H2
as
terminal
reducing
agent
source
hydrides
forging
bonds.
In
this
way,
approach
gives
rise
bond-forming
reactions
3d
metal
need
stoichiometric
organometallic
agent.
