Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Янв. 30, 2024
Abstract
The
combination
of
achiral
Cp*Rh(III)
with
chiral
carboxylic
acids
(CCAs)
represents
an
efficient
catalytic
system
in
transition
metal‐catalyzed
enantioselective
C−H
activation.
However,
this
hybrid
catalysis
is
limited
to
redox‐neutral
activation
reactions
and
the
adopt
oxidative
remains
elusive
pose
a
significant
challenge.
Herein,
we
describe
development
electrochemical
Cp*Rh(III)‐catalyzed
annulation
sulfoximines
alkynes
enabled
by
acid
(CCA)
operationally
friendly
undivided
cell
at
room
temperature.
A
broad
range
enantioenriched
1,2‐benzothiazines
are
obtained
high
yields
excellent
enantioselectivities
(up
99
%
yield
98
:
2
er).
practicality
method
demonstrated
scale‐up
reaction
batch
reactor
external
circulation.
crucial
intermediate
isolated,
characterized,
transformed,
providing
rational
support
for
Rh(III)/Rh(I)
electrocatalytic
cycle.
Chemical Reviews,
Год журнала:
2021,
Номер
121(8), С. 4805 - 4902
Опубликована: Март 27, 2021
Atropisomerism
is
a
stereochemical
behavior
portrayed
by
three-dimensional
molecules
that
bear
rotationally
restricted
σ
bond.
Akin
to
the
well-represented
point-chiral
molecules,
atropisomerically
chiral
compounds
are
finding
increasing
utilities
in
many
disciplines
where
molecular
asymmetry
influential.
This
provides
steady
demand
on
atroposelective
synthesis,
numerous
synthetic
pursuits
have
been
rewarded
with
conceptually
novel
and
streamlined
methods
while
expanding
structural
diversity
of
atropisomers.
review
summarizes
key
achievements
stereoselective
preparation
biaryl,
heterobiaryl,
nonbiaryl
atropisomers
documented
between
2015
2020.
Emphasis
placed
strategies
for
each
class,
examples
cited
illustrate
potential
applications
accessed
atropochiral
targets.
ACS Central Science,
Год журнала:
2021,
Номер
7(2), С. 245 - 261
Опубликована: Фев. 2, 2021
Since
the
definition
of
"12
Principles
Green
Chemistry"
more
than
20
years
ago,
chemists
have
become
increasingly
mindful
need
to
conserve
natural
resources
and
protect
environment
through
judicious
choice
synthetic
routes
materials.
The
direct
activation
functionalization
C–H
bonds,
bypassing
intermediate
functional
group
installation
is,
in
abstracto,
step
atom
economic,
but
numerous
factors
still
hinder
sustainability
large-scale
applications.
In
this
Outlook,
we
highlight
research
areas
seeking
overcome
challenges
activation:
pursuit
abundant
metal
catalysts,
avoidance
static
directing
groups,
replacement
oxidants,
introduction
bioderived
solvents.
We
close
by
examining
progress
made
subfield
aryl
borylation
from
its
origins,
highly
efficient
precious
Ir-based
systems,
emerging
3d
catalysts.
future
growth
field
will
depend
on
industrial
uptake,
thus
urge
researchers
strive
toward
sustainable
activation.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(35), С. 14025 - 14040
Опубликована: Авг. 25, 2021
Transition-metal-catalyzed
enantioselective
C-H
functionalization
has
become
a
powerful
strategy
for
the
formation
of
C-C
or
C-X
bonds,
enabling
highly
asymmetric
synthesis
wide
range
enantioenriched
compounds.
Atropisomers
are
widely
found
in
natural
products
and
pharmaceutically
relevant
molecules,
have
also
applications
as
privileged
frameworks
chiral
ligands
catalysts.
Thus,
research
into
routes
atropisomers
garnered
great
interest
recent
years.
In
this
regard,
transition-metal-catalyzed
emerged
an
atom-economic
efficient
toward
their
synthesis.
Perspective,
approaches
by
reactions
summarized.
The
main
focus
here
is
on
catalysis
via
Pd,
Rh,
Ir
complexes,
which
been
most
frequently
utilized
catalysts
among
reported
reactions.
Finally,
we
discuss
limitations
available
protocols
give
outlook
possible
future
avenues
research.
Chemical Reviews,
Год журнала:
2021,
Номер
122(3), С. 3180 - 3218
Опубликована: Ноя. 19, 2021
Synthetic
organic
electrosynthesis
has
grown
in
the
past
few
decades
by
achieving
many
valuable
transformations
for
synthetic
chemists.
Although
electrocatalysis
been
popular
improving
selectivity
and
efficiency
a
wide
variety
of
energy-related
applications,
last
two
decades,
there
much
interest
to
develop
conceptually
novel
transformations,
selective
functionalization,
sustainable
reactions.
This
review
discusses
recent
advances
combination
electrochemistry
homogeneous
transition-metal
catalysis
synthesis.
The
enabling
mechanistic
studies
are
presented
alongside
advantages
as
well
future
directions
address
challenges
metal-catalyzed
electrosynthesis.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(32), С. 13451 - 13457
Опубликована: Апрель 3, 2020
Abstract
Asymmetric
pallada‐electrocatalyzed
C−H
olefinations
were
achieved
through
the
synergistic
cooperation
with
transient
directing
groups.
The
electrochemical,
atroposelective
activations
realized
high
position‐,
diastereo‐,
and
enantio‐control
under
mild
reaction
conditions
to
obtain
highly
enantiomerically‐enriched
biaryls
fluorinated
N−C
axially
chiral
scaffolds.
Our
strategy
provided
expedient
access
to,
among
others,
novel
BINOLs,
dicarboxylic
acids
helicenes
of
value
asymmetric
catalysis.
Mechanistic
studies
by
experiments
computation
key
insights
into
catalyst's
mode
action.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(22), С. 9872 - 9878
Опубликована: Май 11, 2020
A
scalable
enantioselective
nickel-catalyzed
electrochemical
reductive
homocoupling
of
aryl
bromides
has
been
developed,
affording
enantioenriched
axially
chiral
biaryls
in
good
yield
under
mild
conditions
using
electricity
as
a
reductant
an
undivided
cell.
Common
metal
reductants
such
Mn
or
Zn
powder
resulted
significantly
lower
yields
the
absence
electric
current
otherwise
identical
conditions,
underscoring
enhanced
reactivity
provided
by
combination
transition
catalysis
and
electrochemistry.
