Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
137(1)
Published: Nov. 7, 2024
Abstract
Precise
synthesis
of
carboxylic
acids
via
catalytic
carboxylation
with
CO
2
is
highly
appealing.
Although
considerable
advancements
have
been
achieved
in
difunctionalizing
unsaturated
hydrocarbons,
the
asymmetric
variants
are
conspicuously
underdeveloped,
particularly
addressing
axially
chiral
alkenes.
Herein,
we
report
first
atroposelective
alkynes
.
A
variety
valuable
obtained
good
yields
and
high
chemo‐,
regio‐,
Z/E
enantio‐selectivities.
Notably,
an
unexpected
anti
‐selective
carbo‐carboxylation
observed
sp
‐hybrid
carbo‐electrophile‐initiated
reductive
alkynes.
Mechanistic
studies
including
DFT
calculation
elucidate
origin
induction
‐selectivity
vinyl‐carboxylation
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 17, 2025
Direct
synthesis
of
enantioenriched
scaffolds
with
multiple
adjacent
stereocenters
remains
an
important
yet
challenging
task.
Herein,
we
describe
a
highly
diastereo-
and
enantioselective
Cu-catalyzed
alkylboration
cyclopropenes,
less
reactive
alkyl
iodides
as
electrophiles,
for
the
efficient
tetra-substituted
borylated
cyclopropanes
bearing
three
consecutive
stereocenters.
This
protocol
features
mild
conditions,
broad
substrate
scope,
good
functional
group
tolerance,
affording
array
chiral
in
to
high
yields
excellent
enantioselectivities.
Detailed
mechanistic
experiments
kinetic
studies
were
conducted
elucidate
reaction
pathway
rate-determining
step
reaction.
DFT
calculations
revealed
that
π···π
stacking
interaction
between
phenyl
groups
on
phosphorus
ligand,
along
smaller
distortion
CuL-Bpin
part,
contributed
The
synthetic
utility
was
showcased
by
facile
some
valuable
centers.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(1)
Published: Aug. 16, 2024
Herein,
we
report
a
synergistic
photoredox/palladium
catalytic
system
for
the
efficient
enantioconvergent
synthesis
of
axially
chiral
esters
from
racemic
heterobiaryl
(pseudo)halides
(bromides/triflates)
with
CO
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
A
three-component
cascade
boronation–dearomatization
reaction
of
alkenes,
a
diboron
compound,
and
pyridinium
salt
is
diclosed,
affording
chiral
boron-containing
1,4-dihyropyridines
in
high
yields
(≤98%)
diastereoselectivity
(≤10:1
dr),
along
with
excellent
enantioselectivity
(typically
>99%
ee).
The
catalytic
system
performs
efficiently
at
low
catalyst
loadings
(1
mol
%)
was
tested
>50
examples,
including
some
biologically
active
molecules.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(3), P. 603 - 603
Published: Jan. 29, 2025
Enantiopure
turbo
chirality
in
small
organic
molecules,
without
other
chiral
elements,
is
a
fascinating
topic
that
has
garnered
significant
interest
within
the
chemical
and
materials
science
community.
However,
further
research
into
application
of
this
concept
have
been
severely
limited
by
lack
effective
asymmetric
tools.
To
date,
only
few
enantiomers
targets
isolated,
these
were
obtained
through
physical
separation
using
HPLC,
typically
on
milligram
scales.
In
work,
we
report
first
approach
to
enantiopure
absence
elements
such
as
central
axial
chirality.
This
demonstrated
assembling
aromatic
phosphine
oxides,
where
three
propeller-like
groups
are
anchored
P(O)
center
via
axes.
Asymmetric
induction
was
successfully
carried
out
sulfonimine
auxiliary,
with
absolute
configurations
conformations
unambiguously
determined
X-ray
diffraction
analysis.
The
resulting
frameworks
exhibit
propellers
arranged
either
clockwise
(P,P,P)
or
counterclockwise
(M,M,M)
configuration.
arrangements,
bulkier
sides
rings
oriented
toward
oxygen
atom
P=O
bond
rather
than
opposite
direction.
Additionally,
orientational
configuration
controlled
auxiliary
well,
showing
one
Naph
pushed
away
from
group
(-CH2-NHSO2-tBu)
phenyl
ring.
Computational
studies
conducted
relative
energies
for
rotational
barriers
target
along
axis
transition
pathway
between
two
enantiomers,
meeting
our
expectations.
work
expected
impact
fields
chemistry,
biomedicine,
future.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 21, 2025
Carboxylation
with
CO2
offers
an
attractive
and
sustainable
access
to
valuable
carboxylic
acids.
Among
these
methods,
direct
C−H
carboxylation
of
terminal
alkynes
has
attracted
much
attention
for
one-carbon
homologation
alkynes,
enabling
rapid
synthesis
propiolic
In
contrast,
the
multi-carbons
construct
important
non-conjugated
alkynyl-containing
acids
not
been
reported.
Herein,
we
present
alkynylcarboxylation
alkenes
via
photoredox
copper
dual
catalysis.
This
protocol
provides
a
practical
method
form
alkynyl
from
readily
available
CO2.
Additionally,
this
approach
also
features
mild
(room
temperature,
1
atm
CO2)
redox-neutral
conditions,
high
atom
step
economy,
good
functional
group
tolerance,
selectivities.
Moreover,
diverse
transformations
β-alkynyl
acid
products
bioactive
molecule
(GPR40/FFA1
agonist)
further
illustrate
synthetic
utility
methodology.
The
report
multi-carbon
is
rare.
authors
catalysis,
affording
