Angewandte Chemie,
Год журнала:
2023,
Номер
135(52)
Опубликована: Ноя. 21, 2023
Abstract
Axially
chiral
diaryl
ethers,
a
distinguished
class
of
atropisomers
possessing
unique
dual
C−O
axis,
hold
immense
potential
for
diverse
research
domains.
In
contrast
to
the
catalytic
enantioselective
synthesis
conventional
single
axis
bearing
atropisomers,
atroposelective
axially
ethers
containing
flexible
remains
significant
challenge.
Herein,
we
demonstrate
first
N‐heterocyclic
carbene
(NHC)‐catalyzed
via
esterification
dialdehyde‐containing
ethers.
Mechanistically,
reaction
proceeds
NHC‐catalyzed
desymmetrization
strategy
afford
corresponding
ether
in
good
yields
and
high
enantioselectivities
under
mild
conditions.
The
derivatization
synthesized
product
expands
utility
present
access
library
compounds.
temperature
dependency
preliminary
investigations
on
racemization
barrier
bonds
are
also
presented.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Ноя. 2, 2023
With
the
rapid
development
of
asymmetric
catalysis,
demand
for
enantioselective
synthesis
complex
and
diverse
molecules
with
different
chiral
elements
is
increasing.
Owing
to
unique
features
atropisomerism,
catalytic
atropisomers
has
attracted
a
considerable
interest
from
chemical
science
community.
In
particular,
introducing
additional
elements,
such
as
carbon
centered
chirality,
heteroatomic
planar
helical
into
provides
an
opportunity
incorporate
new
properties
axially
compounds,
thus
expanding
potential
applications
atropisomers.
Thus,
it
important
perform
transformations
synthesize
bearing
multiple
elements.
spite
challenges
in
transformations,
recent
years,
chemists
have
devised
powerful
strategies
under
organocatalysis
or
metal
synthesizing
wide
range
enantioenriched
Therefore,
become
emerging
field.
This
review
summarizes
progress
this
field
indicates
challenges,
thereby
promoting
horizon.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(52)
Опубликована: Ноя. 21, 2023
Axially
chiral
diaryl
ethers,
a
distinguished
class
of
atropisomers
possessing
unique
dual
C-O
axis,
hold
immense
potential
for
diverse
research
domains.
In
contrast
to
the
catalytic
enantioselective
synthesis
conventional
single
axis
bearing
atropisomers,
atroposelective
axially
ethers
containing
flexible
remains
significant
challenge.
Herein,
we
demonstrate
first
N-heterocyclic
carbene
(NHC)-catalyzed
via
esterification
dialdehyde-containing
ethers.
Mechanistically,
reaction
proceeds
NHC-catalyzed
desymmetrization
strategy
afford
corresponding
ether
in
good
yields
and
high
enantioselectivities
under
mild
conditions.
The
derivatization
synthesized
product
expands
utility
present
access
library
compounds.
temperature
dependency
preliminary
investigations
on
racemization
barrier
bonds
are
also
presented.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(4)
Опубликована: Ноя. 29, 2023
Axially
chiral
diaryl
ethers
are
present
in
numerous
natural
products
and
bioactive
molecules.
However,
only
few
catalytic
enantioselective
approaches
have
been
established
to
access
ether
atropisomers.
Herein,
we
report
the
N-heterocyclic
carbene-catalyzed
synthesis
of
axially
via
desymmetrization
prochiral
2-aryloxyisophthalaldehydes
with
aliphatic
alcohols,
phenol
derivatives,
heteroaromatic
amines.
This
reaction
features
mild
conditions,
good
functional
group
tolerance,
broad
substrate
scope
excellent
enantioselectivity.
The
utility
this
methodology
is
illustrated
by
late-stage
functionalization,
gram-scale
synthesis,
diverse
enantioretentive
transformations.
Control
experiments
DFT
calculations
support
association
NHC-catalyzed
following
kinetic
resolution
enhance
Green Chemistry,
Год журнала:
2024,
Номер
26(5), С. 2705 - 2711
Опубликована: Янв. 1, 2024
A
novel
synthetic
strategy
to
access
strained
heterocycles
is
revealed
through
photocatalysed
annulative
formal
4-
endo-dig
cyclization
of
propargyl
alcohols/amines
with
benzoquinones
under
catalyst/reagent-free
conditions
using
non-hazardous
solvent.
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 922 - 927
Опубликована: Янв. 24, 2024
A
straightforward
methodology
for
the
enantioselective
preparation
of
axially
chiral
2-naphthylpyrroles
has
been
developed.
This
protocol
is
based
on
a
CuI/Fesulphos-catalyzed
highly
1,3-dipolar
cycloaddition
an
azomethine
ylide
followed
by
pyrrolidine
alkylation
and
to
pyrrole
oxidation.
The
mild
conditions
employed
in
DDQ/blue
light-mediated
aromatization
process
facilitate
effective
central-to-axial
chirality
transfer
affording
corresponding
pyrroles
with
high
atroposelectivity.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 5993 - 6001
Опубликована: Янв. 1, 2024
Axially
chiral
molecular
scaffolds
are
widely
present
in
therapeutic
agents,
natural
products,
catalysts,
and
advanced
materials.
The
construction
of
such
molecules
has
garnered
significant
attention
from
academia
industry.
catalytic
asymmetric
synthesis
axially
biaryls,
along
with
other
non-biaryl
molecules,
been
extensively
explored
the
past
decade.
However,
atroposelective
C-O
axial
chirality
remains
largely
underdeveloped.
Herein,
we
document
a
copper-catalyzed
compounds
using
novel
1,8-naphthyridine-based
ligands.
Mechanistic
investigations
have
provided
good
evidence
support
mechanism
involving
synergistic
interplay
between
desymmetrization
reaction
kinetic
resolution
process.
method
described
this
study
holds
great
significance
for
compounds,
promising
applications
organic
chemistry.
utilization
ligands
copper
catalysis
is
anticipated
to
find
broad
copper(i)-catalyzed
azide-alkyne
cycloadditions
(CuAACs)
beyond.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 5, 2025
Photoredox
catalysis
has
emerged
as
a
powerful
tool
for
forming
and
breaking
chemical
bonds,
further
taking
hold
with
its
integration
asymmetric
catalysis.
While
the
dual-catalytic
approach
led
to
successful
examples
of
control
stereogenic
centers,
axes
remained
underexplored.
In
this
study,
an
acylimine
intermediate
was
generated
through
photoredox
catalysis,
symmetric
substrate,
2-arylresorcinol,
desymmetrized
aid
chiral
phosphoric
acid
Using
approach,
center
axis
were
successfully
controlled
provide
natural-product-driven
compound.
The
origins
enantioselectivity
diastereoselectivity
investigated
density
functional
theory
study
four
possible
enantiodetermining
transition
states.
Consequently,
first
total
syntheses
ring-contracted
naphthylisoquinoline
alkaloid
ancistrobrevolines
A
B
accomplished
concisely.
This
provides
not
only
novel
methodology
strategy
synthesize
alkaloids
but
also
direction
advance
catalytic
research
synthesis
studies.
