ABSTRACT:
We
report
a
highly
enantioselective
intermolecular
silylation
of
the
propargylic
C(sp3)−H
bonds
alkynes
for
formation
silanes.
The
optimized
protocol
afforded
enantioenriched
α-silylated
in
good
to
high
yield
with
excellent
levels
stereocontrol
under
mild
conditions.
A
variety
silyl
triflates,
either
commercial
or
situ-generated,
were
used
as
reagents,
and
broad
range
simple
functionalized
alkynes,
including
aryl
alkyl
acetylenes,
dialkyl
1,3-enynes,
successfully
employed
substrates.
In
case
acetylene
substrates,
took
place
regi-oselective
manner.
Preliminary
mechanistic
experiments
suggest
catalytic
cycle
which
electrophilic
addition
triflate
reagent
Ir
center
subsequent
deprotonation
dicationic
Ir–alkyne
complex
are
key
steps.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4275 - 4283
Published: Jan. 1, 2024
A
copper-catalyzed
enantioselective
four-component
reaction
via
the
insertion
of
sulfur
dioxide
toward
synthesis
chiral
sulfones
bearing
an
all-carbon
quaternary
stereocenter
at
β
position
is
reported.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(16), P. 10887 - 10894
Published: Aug. 3, 2023
The
practical
synthesis
of
C-stereogenic
α-aminophosphine
oxides,
which
exhibit
a
wide
range
applications
in
medicinal
chemistry,
biochemistry,
material
science,
and
asymmetric
catalysis,
represents
an
unmet
need.
Herein,
Ni/(S,S)-BenzP*
catalyst
system
is
developed
for
branched
oxides
through
enantioselective
Markovnikov
addition
H-phosphine
to
2-azadienes.
A
variety
readily
available
2-azadienes
undergo
hydrophosphinylation
with
high
enantioselectivities
(up
99%)
good
yields
96%).
These
products
can
be
hydrolyzed
afford
synthetically
valuable
chiral
are
key
building
blocks
the
bioactive
compounds
(such
as
phospholeucine
synthesized
herein),
organocatalysts,
ligands.
Mechanistic
studies
suggest
hydrofunctionalization
process.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(20), P. 7789 - 7794
Published: Jan. 1, 2024
A
copper-catalyzed
highly
regioselective
remote
boryl-
or
silyl-cupration
of
allenynes,
providing
an
efficient
protocol
for
the
synthesis
conjugated
allene-substituted
alkenyl
boronates
silanes,
has
been
developed.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(23), P. 16194 - 16202
Published: June 4, 2024
Although
progress
has
been
made
in
enantioselective
hydroboration
of
di-
and
trisubstituted
alkenes
over
the
past
decades,
tetrasubstituted
with
high
diastereo-
enantioselectivities
continues
as
an
unmet
challenge
since
1950s
due
to
its
extremely
low
reactivity
difficulties
simultaneously
control
regio-
stereoselectivity
a
alkene.
Here,
we
report
highly
regio-,
diastereo-,
catalytic
diverse
acyclic
alkenes.
The
delicate
interplay
electron-rich
rhodium
complex
coordination-assistance
forms
adaptive
catalyst
that
effectively
overcomes
controls
stereoselectivity.
generality
system
is
exemplified
by
efficacy
across
various
steric
electronic
properties.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(31), P. 5703 - 5708
Published: July 31, 2023
Herein
we
report
an
iridium(I)-catalyzed
atroposelective
alkenylation
of
isoquinoline-derived
heterobiaryls
with
terminal
alkynes.
In
the
presence
a
cationic
iridium(I)
catalyst
(R)-SEGPHOS
as
chiral
ligand,
this
atom-economical
protocol
allows
rapid
construction
series
axially
alkenylated
in
moderate
to
good
yields
high
enantioselectivities.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(18)
Published: Aug. 2, 2023
Abstract
A
facile
enantioselective
alkynylation
of
cyclic
ketimines
attached
to
a
neutral
functional
group
utilizing
the
dual
Cu(I)‐CPA
catalysis
is
described.
The
strategy
2‐aryl‐3
H
‐indol‐3‐one
directly
chiral
propargylic
amines
containing
indolin‐3‐one
moiety
in
good
yields
and
enantioselectivities.
Moreover,
gram‐scale
synthesis
propargylamines
based
C2‐quaternary
indolin‐3‐ones
was
performed.
synthetic
applications
were
confirmed
by
transformations
products
with
no
decrease
yield
enantioselectivity.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 4, 2024
Comprehensive
Summary
Herein,
an
unprecedented
nickel‐catalyzed
regioselective
hydroalkynylation
of
unsymmetrical
internal
alkynes
was
realized
with
steric
hindered
resistance
selectivity
via
the
cyano‐directing
group
strategy.
Significantly,
resulting
1,3‐enyne
products
could
be
effectively
employed
in
synthesis
novel
nitrogen‐containing
tricyclics
compounds,
that
provided
potential
candidate
compound
8a
(IC
50
=
2.6—6.1
μmol/L)
for
anti‐tumor
cell
proliferation
activity.
Therefore,
this
work
not
only
improves
transition‐metal‐
catalyzed
strategy
alkynes,
but
also
exhibits
versatility
1,3‐enynes
construction
complex
bioactive
chemical
space.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(1), P. 29 - 34
Published: Sept. 11, 2023
Comprehensive
Summary
Alkynes
are
versatile
synthons
in
organic
synthesis,
as
well
important
structural
moieties
bioactive
molecules.
Recently,
transition
metal‐catalyzed
hydroalkynylation
of
alkenes
has
been
developed
with
reactive
and
bearing
directing
groups.
However,
the
regioselective
simple
is
still
challenging.
Herein,
we
have
a
palladium‐catalyzed
Markovnikov
unactivated
terminal
alkenes,
which
provides
an
efficient
approach
for
synthesis
branched
alkynyl
compounds
under
mild
conditions.
This
reaction
features
excellent
functional
group
tolerance,
good
yields
regioselectivity.
Moreover,
asymmetric
also
achieved
moderate
enantioselectivity
by
introducing
sterically
bulky
chiral
Pyox
ligand.
Synlett,
Journal Year:
2023,
Volume and Issue:
35(10), P. 1160 - 1164
Published: Nov. 16, 2023
Abstract
A
hydroalkynylation
reaction
of
1,3-dienes
with
simple
alkynes,
facilitated
by
an
efficient
nickel
catalyst
system
the
9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene
(Xantphos)
ligand,
is
presented.
This
displays
a
broad
substrate
range
for
encompassing
both
aryl
alkynes
and
alkyl
thereby
overcoming
previous
constraints
in
1,3-diene
hydroalkynylation.
The
method
offers
convenient
direct
means
obtaining
allylic
high
atom
step
economy.
