Abstract
In
recent
years,
there
has
been
growing
interest
in
utilizing
carbon
dioxide
as
a
feedstock
for
organic
synthesis
due
to
its
abundance,
low
cost,
and
environmentally
benign
nature,
with
particular
focus
on
the
catalytic
of
alkanoic
acids
from
readily
available
starting
materials
via
C–C
bond
formation.
This
review
provides
comprehensive
overview
this
approach,
covering
alkyl
(pseudo)halides,
alcohol
derivatives,
isolable
organometallic
species,
alkenes,
alkanes
C(sp3)–H
activation.
The
versatility
practicality
demonstrated
these
methods
underscores
significance
approach
accessing
valuable
carboxylic
acid
derivatives
dioxide.
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
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(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.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(11), P. 1901 - 1906
Published: March 9, 2023
A
nickel-catalyzed
enantio-
and
regioconvergent
alkylation
of
regioisomeric
mixtures
racemic
germylated
allylic
electrophiles
with
alkyl
nucleophiles
is
reported.
Key
to
success
a
newly
developed
hept-4-yl-substituted
Pybox
ligand
that
enables
accessing
various
chiral
γ-germyl
α-alkyl
building
blocks
in
excellent
yields
enantioselectivities.
The
reason
for
the
regioconvergence
steering
effect
bulky
germyl
group.
resulting
vinyl
germanes
can
be
easily
halodegermylated
without
racemization
stereocenter
afford
synthetically
valuable
γ-stereogenic
halides.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(31)
Published: June 2, 2023
Abstract
Chiral
amines
are
broadly
used
compounds
in
pharmaceutical
industry
and
organic
synthesis,
reductive
amination
reactions
have
been
the
most
appreciated
methods
for
their
syntheses.
However,
one‐step
transfer
hydrogenative
direct
asymmetric
(THDARA)
that
could
expand
scope,
simplify
operation
eliminate
use
of
additives
has
challenging.
In
this
work,
based
on
Xiao's
racemic
2010
our
recent
work
novel
chiral
pyridine
ligands,
half‐sandwich
iridium
catalysts
were
rationally
designed
synthesized.
Using
optimized
catalyst
azeotropic
mixture
formic
acid
triethylamine
as
hydrogen
source,
a
broad
range
α‐chiral
(hetero)aryl
amines,
including
various
polar
functional
groups
heterocycles,
prepared
generally
high
yield
enantioselectivity
under
mild
operationally
simple
conditions.
Density
theory
(DFT)
calculation
catalytically
active
Ir−H
species
key
hydride
step
supported
pyridine‐induced
stereospecific
generation
center,
enantioselection
by
taming
highly
flexible
transition
structure
with
multiple
attractive
non‐covalent
interactions.
This
introduced
type
effective
simplified
approach
to
medicinally
important
well
rare
example
robust
enantioselective
transition‐metal
catalysis.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 18823 - 18830
Published: July 1, 2024
The
catalytic
regio-
and
enantioselective
hydrocarboxylation
of
alkenes
with
carbon
dioxide
is
a
straightforward
strategy
to
construct
enantioenriched
α-chiral
carboxylic
acids
but
remains
big
challenge.
Herein
we
report
the
first
example
highly
enantio-
site-selective
remote
wide
range
readily
available
unactivated
abundant
renewable
CO
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
137(1)
Published: Aug. 16, 2024
Abstract
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
2
and
alkyl
bromides
under
mild
conditions.
A
wide
range
were
obtained
in
good
to
high
yields
excellent
enantioselectivities.
Detailed
mechanistic
studies
unveiled
that
ratio
photocatalyst
palladium
catalyst
exhibited
significant
impact
on
chemo‐
enantioselectivities
reaction.
Kinetic
control
experiments
supported
proposed
mechanism
involving
cascade
asymmetric
carboxylation
followed
by
S
N
substitution.
The
achievement
enantioselectivity
relies
not
only
choice
metallaphotoredox
catalysts
but
also
utilization
bromides,
which
trap
generated
carboxylic
anions
situ,
thus
preventing
their
immediate
racemization.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(38), P. 6959 - 6963
Published: Sept. 20, 2023
The
cross-coupling
of
epoxides
with
acyl
chlorides
or
anhydrides
by
a
nickel/titanocene
dual
catalytic
system
is
established.
A
variety
synthetically
useful
β-hydroxy
ketones
were
obtained
in
good
to
high
yields
using
modified
pyridine-oxazoline
ligand.
reaction
proceeds
via
the
cooperation
titanocene-catalyzed
ring-opening
and
nickel-catalyzed
acylation
benzylic
radical
intermediate.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(14), P. 10199 - 10205
Published: July 11, 2023
In
this
context,
we
successfully
utilize
polycyclic
aryl-activated
alkyl
ammonium
triflates
as
the
electrophilic
alkylating
agent
in
nickel-catalyzed
hydroxyl-
or
sulfonamide-directed
cross-electrophile
coupling
reaction
with
an
array
of
phenyl
benzoates,
allowing
for
synthesis
various
aryl
ketones
under
mild
conditions.
