Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 9, 2023
The
C-N
axially
chiral
N-arylpyrrole
motifs
are
privileged
scaffolds
in
numerous
biologically
active
molecules
and
natural
products,
as
well
ligands/catalysts.
Asymmetric
synthesis
of
N-arylpyrroles,
however,
is
still
challenging,
the
simultaneous
creation
contiguous
axial
central
chirality
remains
unknown.
Herein,
a
diastereo-
atroposelective
N-arylpyrroles
enabled
by
light-induced
phosphoric
acid
catalysis
has
been
developed.
key
transformation
one-pot,
three-component
oxo-diarylation
reaction,
which
simultaneously
creates
quaternary
stereogenic
center.
A
broad
range
unactivated
alkynes
were
readily
employed
reaction
partner
this
transformation,
products
obtained
good
yields,
with
excellent
enantioselectivities
very
diastereoselectivities.
Notably,
skeletons
represent
interesting
structural
that
could
be
used
ligands
catalysts
asymmetric
catalysis.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(8), P. 4805 - 4902
Published: March 27, 2021
Atropisomerism
is
a
stereochemical
behavior
portrayed
by
three-dimensional
molecules
that
bear
rotationally
restricted
σ
bond.
Akin
to
the
well-represented
point-chiral
molecules,
atropisomerically
chiral
compounds
are
finding
increasing
utilities
in
many
disciplines
where
molecular
asymmetry
influential.
This
provides
steady
demand
on
atroposelective
synthesis,
numerous
synthetic
pursuits
have
been
rewarded
with
conceptually
novel
and
streamlined
methods
while
expanding
structural
diversity
of
atropisomers.
review
summarizes
key
achievements
stereoselective
preparation
biaryl,
heterobiaryl,
nonbiaryl
atropisomers
documented
between
2015
2020.
Emphasis
placed
strategies
for
each
class,
examples
cited
illustrate
potential
applications
accessed
atropochiral
targets.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(17)
Published: Jan. 26, 2022
Abstract
The
first
highly
atroposelective
construction
of
N−N
axially
chiral
indole
scaffolds
was
established
via
a
new
strategy
de
novo
ring
formation.
This
makes
use
the
organocatalytic
asymmetric
Paal–Knorr
reaction
well‐designed
N
‐aminoindoles
with
1,4‐diketones,
thus
affording
‐pyrrolylindoles
in
high
yields
and
excellent
atroposelectivities
(up
to
98
%
yield,
96
ee).
In
addition,
this
is
applicable
for
synthesis
bispyrroles
97
More
importantly,
such
heterocycles
can
be
converted
into
organocatalysts
applications
catalysis,
some
molecules
display
potent
anticancer
activity.
work
not
only
provides
but
also
offers
members
atropisomer
family
promising
synthetic
medicinal
chemistry.
Accounts of Chemical Research,
Journal Year:
2022,
Volume and Issue:
55(19), P. 2780 - 2795
Published: Sept. 19, 2022
ConspectusAtropisomers,
arising
from
conformational
restriction,
are
inherently
chiral
due
to
the
intersecting
dissymmetric
planes.
Since
there
numerous
applications
of
enantiopure
atropisomers
in
catalyst
design,
drug
discovery,
and
material
science,
asymmetric
preparation
these
highly
prized
molecules
has
become
a
flourishing
field
synthetic
chemistry.
A
number
catalysts,
procedures,
novel
concepts
have
been
developed
for
manufacture
atropisomeric
molecules.
However,
intrinsic
properties
different
types
featuring
biaryl,
hetero-biaryl,
or
non-biaryl
architectures,
only
very
few
methods
pass
rigorous
inspection
considered
generally
applicable.
The
development
broadly
applicable
strategy
various
is
challenge.
In
this
Account,
we
summarize
our
recent
studies
on
enantioselective
synthesis
using
vinylidene
ortho-quinone
methides
(VQMs)
as
pluripotent
intermediates.The
most
appealing
features
VQMs
disturbed
aromaticity
axial
chirality
allene
fragment.
At
outset,
organic
neglected
their
principal
liabilities:
ephemeral
nature,
extraordinary
reactivity,
multireaction
sites.
domestication
transient
intermediate
was
demonstrated
by
situ
catalytic
generation
VQMs,
reactivity
selectivity
were
fully
explored
judiciously
modifying
precursors
tuning
systems.
variety
axially
heterocycles
achieved
through
five-,
six-,
seven-
nine-membered
ring
formation
VQM
intermediates
with
kinds
branched
nucleophilic
functional
groups.
C–N
axis
could
be
constructed
via
N-annulation
desymmetrization
preformed
scaffolds.
We
take
advantage
high
electrophilicity
toward
series
sulfur
carbon
based
nucleophiles
leading
vinyl
arenes.
Furthermore,
helical
compounds
realized
cycloaddition
consecutive
annulation
intermediates.
These
achievements
that
work
nuclear
parent
collective
distinct
complex
optically
active
atropisomers.
Recently,
isolation
structural
characterization
elusive
which
questioned
putative
decades.
successful
provided
direct
evidence
existence
an
unprecedented
opportunity
directly
investigate
reactivity.
good
thermal
stability
reserved
isolated
great
potential
reagents
expanded
border
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Jan. 10, 2022
Abstract
Axially
chiral
styrenes
bearing
a
axis
between
sterically
non-congested
acyclic
alkene
and
an
aryl
ring
are
difficult
to
prepare
due
low
rotational
barrier
of
the
axis.
Disclosed
here
is
N
-heterocyclic
carbene
(NHC)
catalytic
asymmetric
solution
this
problem.
Our
reaction
involves
ynals,
sulfinic
acids,
phenols
as
substrates
with
NHC
catalyst.
Key
steps
involve
selective
1,4-addition
anion
acetylenic
acylazolium
intermediate
sequential
E
-selective
protonation
set
up
affords
axially
product
>
99:1
e.r
.,
20:1
/
Z
selectivity,
excellent
yields.
The
sulfone
carboxylic
ester
moieties
in
our
styrene
products
common
bioactive
molecules
catalysis.
Tetrahedron Chem,
Journal Year:
2022,
Volume and Issue:
1, P. 100009 - 100009
Published: March 1, 2022
Axial
chirality
is
historically
epitomized
by
biaryl
compounds
containing
rotationally
impeded
aryl-aryl
linkage.
As
the
field
of
atroposelective
catalysis
advances,
synthesis
and
application
less
common
scaffolds
such
as
alkenes
have
now
come
to
fore.
The
manifestation
axial
in
aryl
was
hypothesized
1928
first
resolution
achieved
nearly
a
decade
later.
However,
catalytic
asymmetric
construction
axially
chiral
open-chain
appeared
only
2017
which
ushered
renewed
focus
on
these
structures.
In
principle,
possess
an
alkene
group
tethered
at
one
end
stereogenic
axis,
greatly
reduces
overall
rigidity.
To
date,
atropisomers
with
C
(vinyl)-C
(aryl)
(vinyl)-heteroatom
bond
been
reported.
Considering
rapid
growth
synthetic
utility
alkenes,
this
review
intends
provide
historical
overview
discusses
new
developments.
It
hope
that
timely
discussion
would
motivate
continued
nascent
field.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(5), P. 1322 - 1345
Published: Jan. 1, 2023
Functionalization
of
alkenes/alkynes
is
a
highly
effective
route
to
achieve
molecular
complexity.
This
review
summarizes
recent
progresses
on
the
1,2-difunctionalization/hydrofunctionalization
unactivated
with
C−S
bond
formation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(10)
Published: Jan. 17, 2024
Abstract
An
efficient
catalytic
asymmetric
electrophilic
sulfenylation
reaction
for
the
synthesis
of
planar‐chiral
sulfur‐containing
cyclophanes
has
been
developed
first
time.
This
was
achieved
by
using
a
new
Lewis
base
catalyst
and
ortho
‐trifluoromethyl‐substituted
sulfenylating
reagent.
Using
substrates
with
low
rotational
energy
barrier,
transformation
proceeded
through
dynamic
kinetic
resolution,
high
barrier
allowed
to
undergo
resolution
process.
Meanwhile,
this
compatible
desymmetrization
process
when
symmetric
were
used.
Various
readily
obtained
in
moderate
excellent
yields
enantioselectivities
(up
97
%
yield
95
ee).
approach
used
synthesize
pharmaceutically
relevant
molecules.
Density
functional
theory
calculations
showed
that
π‐π
interactions
between
sulfenyl
group
aromatic
ring
substrate
play
crucial
role
enantioinduction
reaction.