Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(43)
Published: July 15, 2024
Abstract
A
Pd‐catalyzed
asymmetric
isomerization‐hydroamidocarbonylation
of
amide‐containing
alkenes
was
developed,
affording
a
variety
chiral
α‐alkyl
succinimides
in
moderate
to
good
yields
with
high
enantioselectivities.
The
key
success
introducing
bulky
1‐adamentyl
P
‐substitution
and
2,3,5,6‐tetramethoxyphenyl
group
into
the
rigid
‐chirogenic
bisphosphine
ligand
create
stronger
steric
hinderance
deeper
catalytic
pocket.
By
this
approach,
regio‐
or
stereo‐convergent
synthesis
enantiomeric
from
mixture
olefin
isomers
achieved.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2919 - 2927
Published: Jan. 26, 2024
Dicarboxylic
acids
and
derivatives
are
important
building
blocks
in
organic
synthesis,
biochemistry,
the
polymer
industry.
Although
catalytic
dicarboxylation
with
CO2
represents
a
straightforward
sustainable
route
to
dicarboxylic
acids,
it
is
still
highly
challenging
limited
generation
of
achiral
or
racemic
acids.
To
date,
asymmetric
give
chiral
has
not
been
reported.
Herein,
we
report
first
1,3-dienes
via
Cu
catalysis.
This
strategy
provides
an
efficient
environmentally
benign
high
regio-,
chemo-,
enantioselectivities.
The
copper
self-relay
catalysis,
that
is,
Cu-catalyzed
boracarboxylation
carboxylated
allyl
boronic
ester
intermediates
subsequent
carboxylation
C–B
bonds
dicarboxylates,
key
success
this
dicarboxylation.
Moreover,
protocol
exhibits
broad
substrate
scope,
good
functional
group
tolerance,
easy
product
derivatizations,
facile
synthesis
liquid
crystalline
polyester
drug-like
scaffolds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2888 - 2894
Published: Jan. 26, 2024
Catalytic
asymmetric
carboxylation
of
readily
available
alkenes
with
CO2,
an
abundant
and
sustainable
one-carbon
building
block,
that
gives
access
to
value-added
α-stereogenic
carboxylic
acids
in
atom-
step-economic
manner
is
highly
attractive.
However,
it
has
remained
a
formidable
challenge
for
the
synthetic
community.
Here,
first
example
Cu-catalyzed
regio-
enantioselective
boracarboxylation
reaction
on
various
arylalkenes
diboron
under
atmospheric
pressure
CO2
described,
which
afforded
variety
chiral
β-boron-functionalized
α-aryl
up
87%
yield
97%
ee
mild
conditions.
Importantly,
α-substituted
could
also
be
subject
this
protocol
excellent
enantiopurities,
thereby
rendering
efficient
approach
generation
enantioenriched
α-chiral
all-carbon
quaternary
center.
Moreover,
high
functional
group
tolerance,
scalable
synthesis,
facile
bioactive
compounds,
like
(−)-scopolamine,
(−)-anisodamine,
(−)-tropicamide,
further
demonstrated
utility
strategy.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(25), P. 13603 - 13614
Published: June 6, 2023
Chiral
boronic
esters
are
a
class
of
versatile
building
blocks.
We
describe
herein
an
asymmetric
nickel-catalyzed
borylative
coupling
terminal
alkenes
with
nonactivated
alkyl
halides.
The
success
this
reaction
is
ascribed
to
the
application
chiral
anionic
bisoxazoline
ligand.
This
study
provides
three-component
strategy
access
α-
and
β-stereogenic
from
easily
accessible
starting
materials.
protocol
characterized
by
mild
conditions,
wide
substrate
scope
high
regio-
enantioselectivity.
also
showcase
value
method
in
simplifying
synthesis
several
drug
molecules.
Mechanistic
studies
suggest
that
generation
enantioenriched
bearing
α-stereogenic
center
results
stereoconvergent
process,
while
enantioselectivity-controlling
step
β-stereocenter
switched
olefin
migratory
insertion
due
coordination
ester
group.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 23, 2024
Catalytic
cascade
transformations
of
simple
starting
materials
into
highly
functionalized
molecules
bearing
a
stereochemically
defined
multisubstituted
alkene,
which
are
important
in
medicinal
chemistry,
natural
product
synthesis,
and
material
science,
high
demand
for
organic
synthesis.
The
development
multiple
reaction
pathways
accurately
controlled
by
catalysts
derived
from
different
ligands
is
critical
goal
the
field
catalysis.
Here
we
report
cobalt-catalyzed
strategy
direct
coupling
inexpensive
1,3-enynes
with
two
acrylates
to
construct
diversity
1,3-dienes
containing
trisubstituted
or
tetrasubstituted
olefin.
Such
reactions
can
proceed
through
three
initiated
oxidative
cyclization
achieve
bond
formation
chemo-,
regio-
stereoselectivity
precisely
ligands,
providing
platform
tandem
carbon-carbon
bond-forming
reactions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(51)
Published: Oct. 27, 2022
In
contrast
to
previous
approaches
chiral
α-aryl
carboxylic
acids
that
based
on
reactions
using
hazardous
gases,
pressurized
setup
and
mostly
noble
metal
catalysts,
in
this
work,
a
nickel-catalyzed
general,
efficient
highly
enantioselective
carboxylation
reaction
of
racemic
benzylic
(pseudo)halides
under
mild
conditions
atmospheric
CO2
has
been
developed.
A
unique
2,2'-bipyridine
ligand
named
Me-SBpy
featuring
compact
polycyclic
skeleton
enabled
both
high
reactivity
stereoselectivity.
The
utility
method
demonstrated
by
synthesis
various
(30
examples,
up
95
%
yield
99
:
1
er),
including
profen
family
anti-inflammatory
drugs
transformations
the
as
key
intermediates.
Based
mechanistic
experimental
results,
plausible
catalytic
cycle
involving
Ni-complex/radical
equilibrium
Lewis
acid-assisted
activation
proposed.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: May 31, 2023
Novel
strategy
for
acid
chlorides
formation
that
do
not
use
carboxylic
acids
is
particularly
attractive
in
chemical
synthesis
but
remains
challenging.
Herein,
we
reported
the
development
of
a
highly
effective
Pd-catalyzed
hydrochlorocarbonylation
alkenes
with
CO
alkyl
chlorides.
Chlorosilane
and
AcOH
were
found
as
mild
HCl
source
reaction.
The
reaction
shows
broad
substrate
scope
produces
both
branched
linear
good
to
high
yields
upon
different
ligands
solvents.
Cooperating
follow-up
acylation
reactions,
offers
complementary
platform
diverse
carbonyl
compounds
from
alkenes.
Mechanistic
investigations
suggested
proceeded
though
palladium
hydride
pathway,
prompted
reductive
elimination
acyl-Pd-Cl
intermediate.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 8739 - 8747
Published: May 21, 2024
Asymmetric
tandem
Heck
and
carbonylation
reactions
provide
an
efficient
route
to
synthesize
biologically
important
chiral
cyclic
compounds
with
a
carbonyl
group
have
attracted
increasing
research
interests.
However,
this
type
of
reaction
relies
on
the
initiation
from
oxidative
addition
aryl
halides
or
pseudo
halides,
resulting
in
low
atomic
economy
reaction.
In
addition,
protocol
has
not
adequately
demonstrated
reactivity
generality
heteroarene
halides.
Meanwhile,
asymmetric
Wacker-type
cyclization
are
plagued
by
narrow
substrate
scope
enantioselectivity
remain
underexplored.
Herein,
we
describe
Pd(II)-catalyzed
sequential
1,6-enynes
analogues
carbon
monoxide
(CO).
This
catalytic
system
tolerates
broad
nucleophiles,
including
phenols,
alcohols,
amines.
sequence
forms
four
chemical
bonds,
two
rings,
up
three
stereocenters
single
step.
strategy
allows
for
convenient
access
variety
polycyclic
good
yields
enantio-
diastereoselectivities,
indoles,
benzofurans,
indole-
benzofuran-fused
bicyclo[3.2.1]octanes,
indole-fused
bicyclo[4.2.1]nonane.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 23, 2024
Atropisomeric
biaryls
bearing
carbonyl
groups
have
attracted
increasing
attention
due
to
their
prevalence
in
diverse
bioactive
molecules
and
crucial
role
as
efficient
organo-catalysts
or
ligands
asymmetric
transformations.
However,
preparation
often
involves
tedious
multiple
steps,
the
direct
synthesis
via
carbonylation
has
scarcely
been
investigated.
Herein,
we
report
an
palladium-catalyzed
enantioconvergent
aminocarbonylation
of
racemic
heterobiaryl
triflates
with
amines
dynamic
kinetic
transformation
(DyKAT).
This
protocol
features
a
broad
substrate
scope
excellent
compatibility
for
rapid
construction
axially
chiral
amides
good
high
yields
enantioselectivities.
Detailed
mechanistic
investigations
discover
that
base
can
impede
intramolecular
hydrogen
bond-assisted
axis
rotation
products,
thus
allowing
success
achieve
enantioselectivity.
Moreover,
achieved
be
directly
utilized
N,N,N-pincer
copper-catalyzed
enantioselective
formation
C(sp3)-N
C(sp3)-P
bonds.
Axially
containing
not
only
exist
various
drug
candidates
but
also
serve
authors
transformation.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(4)
Published: Nov. 25, 2022
We
herein
disclose
a
mild
and
efficient
access
to
chiral
3-azabicyclo[3.1.0]hexanes
via
Pd-catalyzed
asymmetric
5-exo-trig
cyclization/cyclopropanation/carbonylation
of
1,6-enynes.
Various
nucleophiles,
such
as
alcohols,
phenols,
amines
water,
are
well
compatible
with
the
reaction
system.
This
forms
three
C-C
bonds,
two
rings,
adjacent
quaternary
carbon
stereocenters
one
C-O/C-N
bond
excellent
regio-
enantioselectivities.
The
products
could
be
further
functionalized
generate
library
3-azabicyclo[3.1.0]hexane
frameworks.