Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(16), P. 5993 - 6001
Published: Jan. 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.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 7, 2025
3-Amino
boron
dipyrromethenes
(BODIPYs)
are
a
versatile
class
of
fluorophores
widely
utilized
in
live
cell
imaging,
photodynamic
therapy,
and
fluorescent
materials
science.
Despite
the
growing
demand
for
optically
active
BODIPYs,
synthesis
chiral
3-amino-BODIPYs,
particularly
catalytic
asymmetric
version,
remains
challenge.
Herein,
we
report
boron-stereogenic
3-amino-BODIPYs
via
palladium-catalyzed
desymmetric
C–N
cross-coupling
prochiral
3,5-dihalogen-BODIPYs.
This
approach
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
remarkable
enantioselectivities,
under
mild
reaction
conditions.
Further
stereospecific
formation
3,5-diamino-BODIPYs,
along
with
an
investigation
into
photophysical
properties
resulting
optical
BODIPYs
also
explored.
protocol
not
only
enriches
chemical
space
chiroptical
BODIPY
dyes
but
contributes
to
realm
chemistry.
(BODIPYs),
which
useful
science,
authors
first
cross-couplings.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(15), P. 6981 - 6991
Published: April 8, 2022
Significant
advances
have
been
achieved
for
the
construction
of
chiral
skeletons
containing
1,2,3-triazoles
via
transition-metal-catalyzed
asymmetric
azide–alkyne
cycloaddition;
however,
most
them
limited
to
terminal
alkynes
in
synthesis
central
chirality
desymmetrization
and
dynamic/dynamic
kinetic
resolution.
Enantioselective
azide-internal-alkyne
cycloaddition
is
extremely
limited.
Moreover,
a
challenging
five-membered
(hetero)biaryl
axially
molecule
still
underexplored.
Herein,
we
first
report
an
atroposelective
atom-economical
1,4,5-trisubstituted
1,2,3-triazoles,
directly
acting
as
core
units
atropisomers,
enantioselective
Rh-catalyzed
(E-RhAAC)
internal
azides.
The
reaction
demonstrates
excellent
functional
group
tolerance,
forging
variety
C–C
under
mild
conditions
with
moderate
yields
(up
99%
yield)
generally
high
enantioselectivities
ee)
along
specific
regiocontrol.
origin
regio-
enantioselectivity
control
disclosed
by
density
theory
(DFT)
calculations,
providing
new
guidance
facile
compounds.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21347 - 21355
Published: Nov. 11, 2022
The
first
copper-catalyzed
enantioselective
[4
+
1]
annulation
of
yne-allylic
esters
with
1,3-dicarbonyl
compounds
was
realized
through
an
elegant
remote
stereocontrol
strategy.
very
ε
regioselective
nucleophilic
substitution
developed
by
employing
a
novel
chiral
copper-vinylvinylidene
species
from
the
new
C4
synthon
esters.
Thus,
greatly
diverse
spirocycles
were
obtained
ample
scope
and
excellent
levels
chemo-,
regio-,
enantioselectivities.
Moreover,
detailed
mechanistic
studies
suggest
Conia-ene
cascade
pathway
on
stereochemical
induction
progress.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: May 12, 2022
Abstract
Compared
with
the
well-developed
carbon-stereogenic
chemistry,
construction
of
boron-stereogenic
compounds
remains
undeveloped
and
challenging.
Herein,
previously
elusive
catalytic
enantioselective
has
been
achieved
through
desymmetric
B–H
bond
insertion
reaction.
The
reaction
2-arylpyridine-boranes
versatile
diazo
under
chiral
copper
catalyst
can
afford
good
to
excellent
enantioselectivity.
Moreover,
synthetic
utility
this
is
demonstrated
by
scalability
downstream
transformations.
DFT
calculations
provide
insights
into
mechanism
origin
stereoselectivity.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(26), P. 3812 - 3820
Published: Jan. 1, 2023
Tetracoordinate
boron
compounds
are
a
highly
important
class
of
molecules,
which
the
key
intermediates
in
many
organoboron-related
chemical
transformations
and
have
unique
luminescence
properties.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(13), P. 4381 - 4391
Published: Jan. 1, 2023
Four-coordinate
organoboron
derivatives
present
interesting
chemical,
physical,
biological,
electronical,
and
optical
properties.
Given
the
increasing
demand
for
synthesis
of
smart
functional
materials
based
on
chiral
compounds,
exploration
stereoselective
boron-stereogenic
organo-derivatives
is
highly
desirable.
However,
construction
compounds
stereogenic
at
boron
has
been
far
less
studied
than
other
elements
main
group
due
to
configurational
stability
concerns.
Nowadays,
these
species
are
no
longer
elusive
configurationally
stable
have
highlighted.
The
idea
show
potential
building
four-coordinate
centre
encourage
future
endeavors
developments
in
field.
