ACS Catalysis,
Год журнала:
2023,
Номер
13(14), С. 9713 - 9723
Опубликована: Июль 11, 2023
The
3d
metallaelectro-catalyzed
C-H
activation
has
been
identified
as
an
increasingly
viable
strategy
to
access
valuable
organic
molecules
in
a
resource-economic
fashion
under
exceedingly
mild
reaction
conditions.
However,
the
development
of
enantioselective
is
very
challenging
and
its
infancy.
Here,
we
disclose
merger
cobaltaelectro-catalyzed
with
asymmetric
catalysis
for
highly
annulation
allenes.
A
broad
range
C-N
axially
chiral
P-stereogenic
compounds
were
thereby
obtained
good
yields
up
98%
high
enantioselectivities
>99%
ee.
practicality
this
approach
was
demonstrated
by
diversification
complex
bioactive
drug
well
decagram
scale
electrocatalysis
continuous
flow.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(47)
Опубликована: Сен. 15, 2022
Enantioselective
C-H
activation
has
surfaced
as
a
transformative
toolbox
for
the
efficient
assembly
of
chiral
molecules.
However,
despite
major
advances
in
rhodium
and
palladium
catalysis,
ruthenium(II)-catalyzed
enantioselective
thus
far
largely
proven
elusive.
In
contrast,
we
herein
report
on
highly
regio-,
diastereo-
alkylation.
The
key
to
success
was
represented
by
identification
novel
C2-symmetric
imidazolidine
carboxylic
acids
(CICAs),
which
are
easily
accessible
one-pot
fashion,
effective
ligands.
This
ruthenium/CICA
system
enabled
installation
central
axial
chirality,
featured
excellent
branched
linear
ratios
with
generally
>20
:
1
dr
up
98
2
er.
Mechanistic
studies
experiment
computation
were
carried
out
understand
catalyst
mode
action.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(10)
Опубликована: Янв. 5, 2022
We
present
herein
our
experimental
and
DFT
computational
studies
on
the
directing
ability
of
chalcogenoether
motifs
in
Pd-catalyzed
atroposelective
C-H
functionalization.
The
thioether
motif
was
found
to
be
a
superior
group
compared
corresponding
ether
selenoether
terms
reactivity
enantiocontrol.
Remarkably,
calculation
provided
predictive
model
for
optimization
reaction
conditions
interpretation
origin
enantioselectivity.
Both
enantioselective
olefination
allylation
reactions
were
successfully
developed
using
chiral
phosphoric
acids
as
efficient
ligands,
providing
broad
range
axially
biaryls
good
yields
with
excellent
enantioselectivities.
highly
enantio-
diastereoselective
construction
polyaryls
bearing
multiple
stereogenic
axes,
gram-scale
various
chemical
transformations
make
this
protocol
more
attractive
significant.
Chemical Science,
Год журнала:
2022,
Номер
13(14), С. 4088 - 4094
Опубликована: Янв. 1, 2022
Thioethers
allowed
for
highly
atroposelective
C-H
olefinations
by
a
palladium/chiral
phosphoric
acid
catalytic
system
under
ambient
air.
Both
N-C
and
C-C
axial
chiral
(hetero)biaryls
were
successfully
constructed,
leading
to
broad
range
of
axially
ACS Catalysis,
Год журнала:
2023,
Номер
13(14), С. 9713 - 9723
Опубликована: Июль 11, 2023
The
3d
metallaelectro-catalyzed
C-H
activation
has
been
identified
as
an
increasingly
viable
strategy
to
access
valuable
organic
molecules
in
a
resource-economic
fashion
under
exceedingly
mild
reaction
conditions.
However,
the
development
of
enantioselective
is
very
challenging
and
its
infancy.
Here,
we
disclose
merger
cobaltaelectro-catalyzed
with
asymmetric
catalysis
for
highly
annulation
allenes.
A
broad
range
C-N
axially
chiral
P-stereogenic
compounds
were
thereby
obtained
good
yields
up
98%
high
enantioselectivities
>99%
ee.
practicality
this
approach
was
demonstrated
by
diversification
complex
bioactive
drug
well
decagram
scale
electrocatalysis
continuous
flow.
