Re-catalyzed
highly
regio-
and
stereoselective
o-C(sp2)–H
silylalkenylation
of
arenes
is
reported
using
a
directing
group
approach
under
ligand-,
additive-,
base-free
conditions.
A
series
imine
groups
(DGs)
have
been
exploited
on
aromatic
aldehydes
to
overcome
de
novo
synthesis.
This
unique
protocol
allows
us
access
o-C–H
activation
various
heterocyclic
moieties,
including
N-aryl
2-pyridones
arylpyridines.
Sequential
difunctionalization
experiments
performed.
mechanistic
carried
out
gain
insight.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(18), С. 6810 - 6816
Опубликована: Апрель 28, 2021
Ru(II)-catalyzed
enantioselective
C-H
functionalization
involving
an
enantiodetermining
cleavage
step
remains
undeveloped.
Here
we
describe
a
activation/annulation
of
sulfoximines
with
α-carbonyl
sulfoxonium
ylides
using
novel
class
chiral
binaphthyl
monocarboxylic
acids
as
ligands,
which
can
be
easily
and
modularly
prepared
from
1,1'-binaphthyl-2,2'-dicarboxylic
acid.
A
broad
range
sulfur-stereogenic
were
in
high
yields
excellent
enantioselectivities
(up
to
99%
yield
ee)
via
desymmetrization,
kinetic
resolution,
parallel
resolution.
Furthermore,
the
resolution
products
transformed
sulfoxides
key
intermediates
for
kinase
inhibitors.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Green Synthesis and Catalysis,
Год журнала:
2022,
Номер
3(2), С. 117 - 136
Опубликована: Янв. 4, 2022
Atropisomeric
C–N
compounds
belong
to
an
important
class
of
axially
chiral
compounds.
However,
whereas
the
asymmetric
synthesis
biaryl
atropisomers
have
been
well
established,
general
and
efficient
strategies
access
single
enantiomers
are
still
rare.
Until
recently,
innovative
methods
developed,
providing
new
opportunities
for
highly
stereoselective
this
vital
atropisomers.
Herein,
we
comprehensively
summarize
development
in
emerging
field
give
some
insights
into
future
advance.
Emphasis
is
placed
on
synthetic
strategies.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(28)
Опубликована: Май 2, 2022
Abstract
Among
sulfoximine
derivatives
containing
a
chiral
sulfur
center,
benzothiadiazine‐1‐oxides
are
important
for
applications
in
medicinal
chemistry.
Here,
we
report
that
the
combination
of
an
achiral
cobalt(III)
catalyst
and
pseudo‐
C
2
‐symmetric
H
8
‐binaphthyl
carboxylic
acid
enables
asymmetric
synthesis
from
sulfoximines
dioxazolones
via
enantioselective
C−H
bond
cleavage.
With
optimized
protocol,
with
several
functional
groups
can
be
accessed
high
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 21, 2023
The
catalytic
asymmetric
construction
of
N-N
atropisomeric
biaryls
remains
a
formidable
challenge.
Studies
them
lag
far
behind
studies
the
more
classical
carbon-carbon
biaryl
atropisomers,
hampering
meaningful
development.
Herein,
first
palladium-catalyzed
enantioselective
C-H
activation
pyrroles
for
synthesis
atropisomers
is
presented.
Structurally
diverse
indole-pyrrole
possessing
chiral
axis
were
produced
with
good
yields
and
high
enantioselectivities
by
alkenylation,
alkynylation,
allylation,
or
arylation
reactions.
Furthermore,
kinetic
resolution
trisubstituted
heterobiaryls
sterically
demanding
substituents
was
also
achieved.
Importantly,
this
versatile
functionalization
strategy
enables
iterative
exquisite
selectivity,
expediting
formation
valuable,
complex,
atropisomers.
Chemical Reviews,
Год журнала:
2023,
Номер
123(17), С. 10641 - 10727
Опубликована: Авг. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4250 - 4260
Опубликована: Март 13, 2023
Herein,
we
disclose
an
efficient
cobalt-catalyzed
enantioselective
C–H
activation
and
annulation
of
benzamides
with
alkenes.
This
transformation
is
facilitated
via
the
commercially
available
cobalt(II)
catalyst
in
presence
easily
prepared
chiral
salicyl-oxazoline
(Salox)
ligand,
which
provides
facile
access
to
(R)
or
(S)
enantiomers
dihydroisoquinolone
derivatives.
It
noticeable
that
reaction
proceeded
efficiently
within
extremely
short
time
from
10
30
min
under
mild
conditions.
A
broad
range
alkenes
bear
various
functional
substituents
have
been
shown
good
compatibility
deliver
targeted
products
high
yields
enantioselectivities
(51
examples,
up
98%
yield
99%
ee).
The
gram
scale
experiment
removal
directing
group
further
demonstrate
practicability
this
protocol
potential
industrial
applications.
Density
theory
calculations
elucidate
mechanism,
spin-state
change
olefin
insertion
step
accelerates
subsequent
C–N
reductive
elimination,
identified
as
stereo-determining
step.
AIM
analysis
indicates
π
interactions
are
vital
for
controlling
switching
stereoselectivity.
ACS Catalysis,
Год журнала:
2021,
Номер
11(15), С. 9151 - 9158
Опубликована: Июль 9, 2021
In
this
report,
distally
disposed
axial
and
central
chirality
has
been
installed
in
a
synergistic
fashion
via
rhodium-catalyzed
C–H
alkylation
of
benzamides
using
N-arylmaleimide
as
the
alkylating
reagent,
which
enantio-
diastereo-determining
steps
are
merged
into
single
one.
The
coupling
system
features
mild
reaction
conditions,
broad
substrate
scope,
excellent
diastereoselectivity.
chiral
induction
enabled
by
judicious
choice
rhodium
cyclopentadienyl
catalyst
that
serves
to
control
both
orientation
olefin
unit
prochiral
C–N
bond.
ACS Catalysis,
Год журнала:
2021,
Номер
11(10), С. 6135 - 6140
Опубликована: Май 6, 2021
The
highly
atroposelective
construction
of
axially
chiral
N-arylindolocarbazoles
is
disclosed
via
the
Rh(II)-catalyzed
intermolecular
carbene
N–H
insertion
reactions.
This
straightforward
transformation
provides
a
rapid
access
to
wide
range
enantio-enriched
N-arylindolocarbazole
atropisomers
bearing
C–N
axis
in
moderate
good
yields
and
high
enantioselectivities.
Also,
synthetic
utility
this
protocol
unambiguously
emphasized
by
late-stage
functionalization
(LSF)
some
representative
natural
products
bioactive
molecules.
Furthermore,
polyaromatic
ring
N-arylindolocarbazole-derived
phosphoric
acid
(CPA)
synthesis
also
highlight
its
practical
value
materials
chemistry
catalytic
asymmetric
synthesis.