Angewandte Chemie,
Год журнала:
2023,
Номер
136(1)
Опубликована: Ноя. 16, 2023
Abstract
Axially
chiral
open‐chained
olefins
are
an
underexplored
class
of
atropisomers,
whose
enantioselective
synthesis
represents
a
daunting
challenge
due
to
their
relatively
low
racemization
barrier.
We
herein
report
rhodium(I)‐catalyzed
hydroarylative
cyclization
1,6‐diynes
with
three
distinct
classes
arenes,
enabling
highly
broad
range
axially
1,3‐dienes
that
conformationally
labile
(Δ
G
≠
(
rac
)=26.6–28.0
kcal/mol).
The
coupling
reactions
in
each
category
proceeded
excellent
enantioselectivity,
regioselectivity,
and
Z/E
selectivity
under
mild
reaction
conditions.
Computational
studies
the
quinoline
N
‐oxide
system
reveal
proceeds
via
initial
oxidative
1,6‐diyne
give
rhodacyclic
intermediate,
followed
by
σ‐bond
metathesis
between
arene
C−H
bond
Rh−C(vinyl)
bond,
subsequent
C−C
reductive
elimination
being
enantio‐determining
turnover‐limiting.
DFT‐established
mechanism
is
consistent
experimental
studies.
coupled
products
‐oxides
undergo
facile
visible
light‐induced
intramolecular
oxygen‐atom
transfer,
affording
epoxides
complete
axial‐to‐central
chirality
transfer.
Chemical Reviews,
Год журнала:
2023,
Номер
123(16), С. 10079 - 10134
Опубликована: Авг. 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,
Год журнала:
2024,
Номер
146(24), С. 16567 - 16580
Опубликована: Июнь 7, 2024
Axially
chiral
biaryls
featuring
a
C–N
axis
are
important
functional
molecules
in
diverse
fields.
The
asymmetric
Buchwald–Hartwig
reaction
represents
powerful
strategy
for
these
targets.
Previous
studies,
however,
have
been
predominantly
restricted
to
intramolecular
atroposelective
coupling,
likely
due
the
steric
and
entropic
effects
reductive
elimination
of
Pd(II)
species
with
sterically
congested
aryl
nitrogen
groups.
We
now
report
two
intermolecular
coupling
systems
bulky
NH
lactams
halohydrocarbons
enabled
by
rerouting
mechanism
one
that
accommodates
challenging
substrates.
Both
exhibited
group
tolerance,
excellent
enantioselectivity,
high
Z
selectivity
(if
applicable),
affording
atropisomeric
biaryl
olefins
through
de
novo
construction
axis.
Experimental
computational
studies
were
performed
elucidate
mechanism,
switch
pathways
is
traced
effect
(ortho
substituent)
halide
substrate.
A
2,6-disubstituted
reorients
proximal
lactamide
ligand
its
unusual
O-ligation
mode.
With
amide
oxygen
participation,
this
intermediate
undergoes
an
accessible
barrier
five-membered
ring
transition
state,
pathway
as
well
induction
mode
has
much
underexplored
catalysis.
Enantioselective
catalysis
is
one
of
the
most
prominent
strategies
in
organic
synthesis
to
access
chiral
bioactive
compounds
and
advanced
materials.
Particularly,
development
ligands
has
significantly
efficiency
selectivity
transition
metal‐catalyzed
enantioselective
transformations.
Over
recent
decades,
numerous
ligand
classes
with
distinct
geometrical
electronic
properties
have
been
established.
Despite
these
advances,
demand
for
novel,
tunable,
highly
effective
persists,
driven
by
need
structurally
diverse
molecules
pursuit
greener,
more
sustainable
catalytic
processes.
Herein,
a
novel
class
oxazoline
ureas
introduced
their
potential
as
κ
2
‐
N
,
O
‐preligands
metal
demonstrated.
The
urea
are
featurized
compared
amide
enol
derivatives
using
physical
descriptors.
A
multivariate
linear
regression
model
constructed
quantitatively
describe
effect
quinoline
fragment
from
substrate
on
enantioselectivity.
Moreover,
effectively
applied
atropo‐enantioselective
cobaltaelectro‐catalyzed
C─H
annulations
1‐alkynyl
indoles.
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13055 - 13064
Опубликована: Авг. 15, 2024
Catalytic
asymmetric
hydrofunctionalization
of
π-bonds
has
been
extensively
studied,
but
the
alkynes
that
affords
atropoisometric
products
remains
heavily
underexplored.
We
herein
report
[Rh(COD)OAc]2/Mg(NTf2)2-catayzed
highly
atroposelective
hydroselenation
two
classes
1-alkynylindoles
using
selenophenols,
where
Mg(II)
salt
both
activates
Rh
catalyst
and
provides
a
key
NTf2
anion
essential
for
catalytic
activity
enantioselectivity,
affording
C–N
axially
chiral
trisubstituted
olefins
bear
relatively
low
racemization
barrier
(ΔG‡
∼
27
kcal/mol).
The
system
features
high
activity,
mild
reaction
conditions,
good
functional
group
tolerance,
regio-,
(E)-,
enantioselectivity.
selenoether
moiety
in
product
framework
can
be
readily
functionalized
to
give
synthetically
useful
products.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(1)
Опубликована: Ноя. 16, 2023
Abstract
Axially
chiral
open‐chained
olefins
are
an
underexplored
class
of
atropisomers,
whose
enantioselective
synthesis
represents
a
daunting
challenge
due
to
their
relatively
low
racemization
barrier.
We
herein
report
rhodium(I)‐catalyzed
hydroarylative
cyclization
1,6‐diynes
with
three
distinct
classes
arenes,
enabling
highly
broad
range
axially
1,3‐dienes
that
conformationally
labile
(Δ
G
≠
(
rac
)=26.6–28.0
kcal/mol).
The
coupling
reactions
in
each
category
proceeded
excellent
enantioselectivity,
regioselectivity,
and
Z/E
selectivity
under
mild
reaction
conditions.
Computational
studies
the
quinoline
N
‐oxide
system
reveal
proceeds
via
initial
oxidative
1,6‐diyne
give
rhodacyclic
intermediate,
followed
by
σ‐bond
metathesis
between
arene
C−H
bond
Rh−C(vinyl)
bond,
subsequent
C−C
reductive
elimination
being
enantio‐determining
turnover‐limiting.
DFT‐established
mechanism
is
consistent
experimental
studies.
coupled
products
‐oxides
undergo
facile
visible
light‐induced
intramolecular
oxygen‐atom
transfer,
affording
epoxides
complete
axial‐to‐central
chirality
transfer.
SynOpen,
Год журнала:
2023,
Номер
07(04), С. 466 - 485
Опубликована: Сен. 6, 2023
Abstract
Transition-metal-catalyzed
enantioselective
C–H
activation
provides
a
straightforward
strategy
to
synthesize
chiral
molecules
from
readily
available
sources.
In
this
graphical
review,
we
summarize
the
progress
on
half-sandwich
d6-metal
(CoIII,
RhIII,
IrIII,
RuII)-catalyzed
functionalization
reactions.
The
review
is
categorized
according
type
of
metal
catalyst
and
ligand
employed.
Representative
enantio-determining
models
catalytic
cycles
are
presented.
Chinese Journal of Organic Chemistry,
Год журнала:
2024,
Номер
44(2), С. 349 - 349
Опубликована: Янв. 1, 2024
Enantioenriched
C-N
axial
chiral
compounds
are
ubiquitous
in
many
important
field,
such
as
natural
products,
drugs
and
ligands.Therefore,
efficient
construction
of
axis
chirality
through
asymmetric
catalytic
synthesis
has
attracted
more
attention
research
interest.In
this
review,
the
recent
progress
been
discussed,
mainly
from
three
aspects:
desymmetrization
prochiral
molecules
or
kinetic
resolution
racemates,
atroposelective
functionalization
axis,
coupling
reaction.The
topic
focuses
on
evolution
system
key
factors
control.The
existing
problems
future
development
direction
field
also
discussed.This
paper
is
a
timely
systematic
review
will
stimulate
extensive
interest.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12559 - 12575
Опубликована: Авг. 27, 2024
The
catalytic
atroposelective
synthesis
of
N–N
axially
chiral
indolylamides
was
established
via
dynamic
kinetic
resolution,
which
makes
use
Lewis
base-catalyzed
asymmetric
acylation
N-acylaminoindoles
as
a
new
type
platform
molecule
with
anhydrides.
By
this
strategy,
series
were
synthesized
in
overall
good
yields
(up
to
98%)
excellent
enantioselectivities
99%
ee).
Moreover,
some
these
display
extent
anticancer
activity,
demonstrates
their
potential
application
medicinal
chemistry.
Therefore,
work
has
not
only
provided
strategy
for
the
monoaryl
indoles
but
also
offered
member
configurational
stability
and
promising
application,
thereby
solving
challenges
indoles.
