Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 26, 2023
Atroposelective
cross-coupling
is
one
of
the
most
appealing
routes
to
construct
axially
chiral
binaphthyl
molecules
due
modular
and
succinct
nature.
Although
transition-metal-catalyzed
cross-couplings
offer
reliable
synthetic
means,
alternative
reaction
modes
that
could
be
applied
broader
substrate
range
without
their
pre-functionalization
highly
desirable.
Herein
we
show
application
Brønsted
acid
catalyst
as
organocatalyst
accomplish
1-azonaphthalenes
2-naphthols
with
high
efficiency,
exclusive
C4-selectivity
well
excellent
enantioselectivity
functional
group
compatibility.
The
identification
acylimidazolinone
auxiliary
for
azo
activating
group,
effective
remote
control
arene
resonance
effect
synergistically
play
key
roles
in
development
this
method.
utility
further
demonstrated
by
transformations
products
into
other
compounds
perfectly
retained
axial
chirality.
Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(20), С. 2938 - 2948
Опубликована: Окт. 4, 2022
ConspectusAtropisomerism
is
a
stereochemical
phenomenon
exhibited
by
molecules
containing
rotationally
restricted
σ
bond.
Contrary
to
classical
point
chirality,
the
two
atropisomeric
stereoisomers
exist
as
dynamic
mixture
and
can
be
interconverted
without
requirement
of
breaking
reforming
Although
this
feature
increases
structural
complexity,
atropisomers
have
become
frequent
targets
in
medicinal
chemistry
projects.
Their
axial
e.g.,
from
axially
chiral
biaryl
motifs,
gives
access
unique
3D
structures.
It
often
desirable
both
enantiomers
via
nonselective
reaction
during
early
discovery
phase
it
allows
team
probe
structure
activity
relationship
directions.
However,
once
single
atropisomer
selected,
presents
several
problems.
First,
pure
may
interconvert
undesired
stereoisomer
under
certain
conditions.
Second,
separation
nontrivial
requires
expensive
stationary
phases
using
chromatography
or
additives
if
salt
resolution
approach
chosen.
Other
options
kinetic
enzymes
catalysts.
apart
high
cost
associated
with
latter
methods,
maximum
yield
only
50%
desired
obtained.
The
ideal
install
axis
enantioselectively
employing
approach.
In
theory,
approaches
potential
provide
quantitative
yield.
This
Account
will
discuss
successes/failures
challenges
we
experienced
developing
methods
for
resolution/separation
asymmetric
synthesis
drug
candidates
one
our
development
Suitability
different
at
various
stages
discussed.
Depending
on
scale
time
available,
was
sometimes
preferred,
whereas
asymmetric-
were
long-term
supply.
With
use
chromatography,
impact
efficiency
solvent
consumption,
depending
nature
substrate,
We
hope
that
readers
get
better
view
process
chemists
meet
when
designing
new
processes
manufacture
atropisomer.
The Chemical Record,
Год журнала:
2023,
Номер
23(7)
Опубликована: Март 21, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
organocatalysis
has
emerged
as
a
powerful
tool
in
the
field
of
modern
organic
synthesis
especially
asymmetric
construction
various
cyclic
skeletons.
As
an
emerging
NHC‐bound
1,3‐bielectrophilic
intermediate,
alkynyl
acylazolium
drawn
substantial
attention
recent
years,
and
been
used
versatile
3C‐synthon
synthesizing
valuable
molecules
since
its
discovery.
In
this
review,
focused
on
different
pathways
for
formation
acylazoliums
from
precursors
like
alkynoic
esters,
acids
ynals,
advances
transformations
applications
pioneered
or
developed
over
last
decade
under
NHC‐catalysis
were
summarized
comprehensively.
At
same
time,
outlook
further
investigation
exploration
novel
reaction
modes
future
was
also
discussed.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16796 - 16811
Опубликована: Июль 20, 2023
Synthetic
application
of
asymmetric
catalysis
relies
on
strategic
alignment
bond
construction
to
creation
chirality
a
target
molecule.
Remote
desymmetrization
offers
distinctive
advantages
spatial
decoupling
catalytic
transformation
and
generation
stereogenic
element.
However,
such
separation
presents
substantial
difficulties
for
the
chiral
catalyst
discriminate
distant
enantiotopic
sites
through
reaction
three
or
more
bonds
away
from
prochirality
center.
Here,
we
report
strategy
that
establishes
acyclic
quaternary
carbon
stereocenters
cross-coupling
reactions
at
distal
positions
aryl
substituents.
The
new
class
amino
acid-derived
ionic
catalysts
enables
desymmetrizing
(enantiotopic-group-selective)
Suzuki-Miyaura
reaction,
Sonogashira
Buchwald-Hartwig
amination
between
diverse
diarylmethane
scaffolds
aryl,
alkynyl,
coupling
partners,
providing
rapid
access
enantioenriched
molecules
project
substituents
widely
spaced
in
three-dimensional
space.
Experimental
computational
investigations
reveal
electrostatic
steering
substrates
by
C-terminus
ligands
interactions.
Cooperative
ion-dipole
interactions
catalyst's
amide
group
potassium
cation
aid
preorganization
transmits
asymmetry
product.
This
study
demonstrates
it
is
practical
achieve
precise
long-range
stereocontrol
engineering
arrangements
catalysts'
substrate-recognizing
groups
metal
centers.
ACS Catalysis,
Год журнала:
2023,
Номер
13(19), С. 12481 - 12493
Опубликована: Сен. 8, 2023
The
crucial
role
of
the
alkoxide
trap
problem
and
impact
oxidation
state
chromium
center
were
demonstrated
on
catalytic
activity
due
to
d-wall
issue.
Through
strategy
surmounting
trap,
a
Cr(0)
catalyst
was
presented
herein
for
efficient
C-alkylation
between
alcohols
via
borrowing
hydrogen/hydrogen
autotransfer.
synthesized
bis-(N-heterocyclic
carbene)-Cr(0)
system
shows
an
performance
(40
examples,
up
96%
yield).
Only
loading
cheap
readily
available
base
NaOH
is
effective
enough
reaction.
Compared
with
Cr(III)/Cr(II),
can
well
avoid
d-p
π
interaction
in
key
metal-alkoxide
intermediate,
thus
overcoming
thermodynamic
sink
problem.
It
plausible
that
Cr(III)
systems
need
be
reduced
Cr(II)
weakening
effect
enhancing
by
using
reductive
strong
bases.
This
should
helpful
development
nonprecious
transition
metal
catalysts.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2403 - 2408
Опубликована: Март 19, 2024
The
catalytic
atroposelective
synthesis
of
axially
chiral
heterobiaryls
was
first
developed
through
the
direct
one-step
dynamic
kinetic
condensation
reaction
with
simple
transformation
C═O
bond
to
C═N
bond,
delivering
a
series
novel
heterobiaryl
oxime
ethers.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 22, 2024
Abstract
A
protocol
for
trans
-hydroboration
of
indole
derivatives
using
heterogeneous
photocatalysis
with
NHC-borane
has
been
developed,
addressing
a
persistent
challenge
in
organic
synthesis.
The
protocol,
leveraging
high
crystalline
vacancy-engineered
polymeric
carbon
nitride
as
catalyst,
enables
diastereoselective
synthesis,
expanding
substrate
scope
and
complementing
existing
methods.
approach
emphasizes
eco-friendliness,
cost-effectiveness,
scalability,
making
it
suitable
industrial
applications,
particularly
renewable
energy
contexts.
catalyst’s
superior
performance,
attributed
to
its
rich
carbon-vacancies
well-ordered
structure,
surpasses
more
expensive
homogeneous
alternatives,
enhancing
viability
large-scale
use.
This
innovation
holds
promise
synthesizing
bioactive
compounds
materials
relevant
medicinal
chemistry
beyond.
Chemical Science,
Год журнала:
2024,
Номер
15(31), С. 12517 - 12522
Опубликована: Янв. 1, 2024
There
has
been
a
recent
upsurge
in
research
aimed
at
synthesizing
inherently
chiral
molecules
devoid
of
point,
axial,
planar
and
helical
chiralities.
We
present
herein
our
design
enantioselective
synthesis
series
macrocycles.
These
compounds,
termed
nor-heteracalixaromatics,
feature
biaryl
bond
that
replaces
one
the
aryl-heteroatom-aryl
linkages
found
classic
heteracalix[4]aromatics.
Macrocyclization
linear
achiral
substrates
