Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(47)
Published: Oct. 16, 2023
Abstract
The
direct
C−H
functionalization
of
1,2‐benzazaborines,
especially
asymmetric
version,
remains
a
great
challenge.
Here
we
report
palladium‐catalyzed
enantioselective
olefination
and
allylation
reactions
1,2‐benzazaborines.
This
approach
is
kinetic
resolution
(KR),
providing
various
C−B
axially
chiral
2‐aryl‐1,2‐benzazaborines
3‐substituted
in
generally
high
yields
with
excellent
enantioselectivities
(selectivity
(S)
factor
up
to
354).
synthetic
potential
this
reaction
showcased
by
late‐stage
modification
complex
molecules,
scale‐up
reaction,
applications.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10079 - 10134
Published: Aug. 1, 2023
This
review
summarizes
the
advancements
in
rhodium-catalyzed
asymmetric
C–H
functionalization
reactions
during
last
two
decades.
Parallel
to
rapidly
developed
palladium
catalysis,
rhodium
catalysis
has
attracted
extensive
attention
because
of
its
unique
reactivity
and
selectivity
reactions.
In
recent
years,
Rh-catalyzed
have
been
significantly
many
respects,
including
catalyst
design,
reaction
development,
mechanistic
investigation,
application
synthesis
complex
functional
molecules.
presents
an
explicit
outline
catalysts
ligands,
mechanism,
scope
coupling
reagents,
applications.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(49), P. 26747 - 26755
Published: Nov. 29, 2023
Herein,
we
report
a
cobalt-catalyzed
atroposelective
reductive
cross-coupling
of
racemic
heterobiaryl
tosylates
with
C(sp2)–X
type
electrophile.
Both
aryl
and
alkenyl
halides
are
competent
precursors
for
this
reaction,
providing
variety
heterobiaryls
as
the
products
in
highly
enantioselective
manner
high
functionality
tolerance.
The
related
asymmetric
arylation
alkenylation
discovered
to
proceed
divergent
mechanisms.
reaction
pathway
changes
from
kinetic
resolution
(KR)
when
bromides
iodides
bearing
strong
electron-withdrawing
substitution
on
para-position
employed
starting
materials
an
enantioconvergent
transformation
via
dynamic
KR
configurationally
labile
cobaltacycles
relatively
electron-rich
used.
change
mechanisms
turns
out
arise
relative
rates
two
competing
elementary
steps,
which
epimerization
cyclic
Co(I)
intermediates
their
trapping
by
coupling
electrophiles
C(sp2)-type
oxidative
addition.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(47)
Published: Oct. 16, 2023
Abstract
The
direct
C−H
functionalization
of
1,2‐benzazaborines,
especially
asymmetric
version,
remains
a
great
challenge.
Here
we
report
palladium‐catalyzed
enantioselective
olefination
and
allylation
reactions
1,2‐benzazaborines.
This
approach
is
kinetic
resolution
(KR),
providing
various
C−B
axially
chiral
2‐aryl‐1,2‐benzazaborines
3‐substituted
in
generally
high
yields
with
excellent
enantioselectivities
(selectivity
(S)
factor
up
to
354).
synthetic
potential
this
reaction
showcased
by
late‐stage
modification
complex
molecules,
scale‐up
reaction,
applications.
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:
2024,
Volume and Issue:
64(1)
Published: Aug. 16, 2024
Herein,
we
report
a
synergistic
photoredox/palladium
catalytic
system
for
the
efficient
enantioconvergent
synthesis
of
axially
chiral
esters
from
racemic
heterobiaryl
(pseudo)halides
(bromides/triflates)
with
CO
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 9, 2025
We
report
an
ether-directed
enantioselective
C(sp2)-H
borylation
catalyzed
by
a
chiral
bidentate
boryl
ligand
(CBL)/iridium
system
for
constructing
axially
biaryls.
This
method
delivered
diverse
biaryls
with
good
to
high
enantioselectivities,
accommodating
varied
electronic
and
steric
substituents
on
the
aryl
rings.
Gram-scale
synthesis
downstream
transformations
of
C-B
bond
underscored
its
practicality.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(63), P. 9646 - 9649
Published: Jan. 1, 2023
Herein,
a
concise
method
for
the
Rh(
iii
)-catalyzed,
directing-group-assisted
C–H/C–H
cross-coupling
of
N-heterocycles
with
other
heteroarenes
is
disclosed
synthesis
unsymmetrical
heterobiaryl
compounds
in
good
to
excellent
yields.
