ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(15), P. 11532 - 11544
Published: July 19, 2024
Glycosyl
donor
activation
emerged
as
an
enabling
technology
for
anomeric
functionalization,
but
aimed
primarily
at
O-glycosylation.
In
contrast,
we
herein
disclose
mechanistically
distinct
electrochemical
glycosyl
bromide
activations
via
halogen-atom
transfer
and
C-glycosylation.
The
radical
addition
to
alkenes
led
C-alkyl
glycoside
synthesis
under
precious
metal-free
reaction
conditions
from
readily
available
bromides.
robustness
of
our
e-XAT
strategy
was
further
mirrored
by
C-aryl
C-acyl
glycosides
assembly
through
nickela-electrocatalysis.
Our
approach
provides
orthogonal
with
expedient
scope,
hence
representing
a
general
method
direct
C-glycosides
assembly.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: June 16, 2023
Abstract
Electrochemistry
utilizes
electrons
as
a
potent,
controllable,
and
traceless
alternative
to
chemical
oxidants
or
reductants,
typically
offers
more
sustainable
option
for
achieving
selective
organic
synthesis.
Recently,
the
merger
of
electrochemistry
with
readily
available
electrophiles
has
been
recognized
viable
increasingly
popular
methodology
efficiently
constructing
challenging
C−C
C‐heteroatom
bonds
in
manner
complex
molecules.
In
this
mini‐review,
we
have
systematically
summarized
most
recent
advances
electroreductive
cross‐electrophile
coupling
(eXEC)
reactions
during
last
decade.
Our
focus
on
electrophiles,
including
aryl
alkyl
(pseudo)halides,
well
small
molecules
such
CO
2
,
SO
D
O.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11518 - 11523
Published: May 16, 2023
The
first
examples
of
enantioselective
doubly
decarboxylative
cross
coupling
are
disclosed.
Malonate
half
amides
smoothly
coupled
to
a
variety
primary
carboxylic
acids
after
formation
the
corresponding
redox-active
esters
under
Ni-electrocatalytic
conditions
using
new
chiral
ligand
based
on
PyBox,
resulting
in
with
α-alkylated
stereocenters.
scope
reaction
is
broad,
tolerating
numerous
functional
groups,
and
uniformly
proceeds
high
ee.
Finally,
potential
utility
this
radical–radical
reductive
simplify
synthesis
demonstrated
case
studies.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(44), P. 23910 - 23917
Published: Oct. 26, 2023
The
merger
of
electrochemistry
and
transition
metal
catalysis
has
emerged
as
a
powerful
tool
to
join
two
electrophiles
in
an
enantioselective
manner.
However,
the
development
electroreductive
cross-couplings
olefins
remains
challenge.
Inspired
by
advantages
synergistic
use
with
nickel
catalysis,
we
present
here
Ni-catalyzed
cross-coupling
acrylates
aryl
halides
alkyl
bromides,
which
affords
chiral
α-aryl
carbonyls
good
excellent
enantioselectivity.
Additionally,
this
catalytic
reaction
can
be
applied
(hetero)aryl
chlorides,
is
difficult
achieve
other
methods.
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
NiI
species
activates
oxidative
addition
bromides
single-electron
transfer.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(5), P. 751 - 762
Published: Feb. 12, 2024
ConspectusAfter
decades
of
palladium
dominating
the
realm
transition-metal-catalyzed
cross-coupling,
recent
years
have
witnessed
exciting
advances
in
development
new
nickel-catalyzed
cross-coupling
reactions
to
form
C(sp3)
centers.
Nickel
possesses
distinct
properties
compared
with
palladium,
such
as
facile
single-electron
transfer
electrophiles
and
rapid
C–C
reductive
elimination
from
NiIII.
These
properties,
among
others,
make
nickel
particularly
well-suited
for
(RCC)
which
two
are
coupled
an
exogenous
reductant
is
used
turn
over
metal
catalyst.
Ni-catalyzed
RCCs
use
readily
available
stable
starting
materials
exhibit
good
functional
group
tolerance,
makes
them
appealing
applications
synthesis
complex
molecules.
Building
upon
foundational
work
by
groups
Kumada,
Durandetti,
Weix,
well
advancements
enantioselective
redox-neutral
cross-couplings
led
Fu
co-workers,
we
initiated
a
program
explore
feasibility
developing
highly
RCCs.
Our
research
has
also
been
driven
keen
interest
unraveling
factors
contributing
enantioinduction
electrophile
activation
seek
avenues
advancing
our
understanding
further
these
reactions.In
first
part
this
Account,
organize
reported
methods
on
basis
identity
electrophiles,
including
benzylic
chlorides,
N-hydroxyphthalimide
(NHP)
esters,
α-chloro
esters
nitriles.
We
highlight
how
selection
specific
chiral
ligands
plays
pivotal
role
achieving
high
cross-selectivity
enantioselectivity.
In
addition,
show
that
reduction
can
be
accomplished
not
only
heterogeneous
reductants,
Mn0,
but
soluble
organic
tetrakis(dimethylamino)ethylene
(TDAE),
electrochemically.
The
homogeneous
TDAE,
suited
studying
mechanism
transformation.
Although
Account
primarily
focuses
RCCs,
using
trifluoroborate
(BF3K)
salts
radical
precursors
dual-Ni/photoredox
systems.At
end
summarize
relevant
mechanistic
studies
closely
related
asymmetric
alkenylation
developed
laboratory
provide
context
between
others.
discuss
ligand
influence
rates
mechanisms
mode
generation
optimize
yield
RCC.
endeavors
offer
insights
intricate
at
play
goal
rate
improve
substrate
scope
anticipate
share
guidance
field.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1522 - 1531
Published: Jan. 3, 2024
The
development
of
a
reliable
strategy
for
stereodivergent
radical
reactions
that
allows
convenient
access
to
all
stereoisomers
homocoupling
adducts
with
multiple
stereogenic
centers
remains
an
unmet
goal
in
organic
synthesis.
Herein,
we
describe
dual-catalyzed
electrooxidative
C(sp3)–H/C(sp3)–H
complete
absolute
and
relative
stereocontrol
the
synthesis
molecules
contiguous
quaternary
stereocenters
general
predictable
manner.
reaction
is
achieved
by
synergistically
utilizing
two
distinct
chiral
catalysts
convert
identical
racemic
substrates
into
inherently
distinctive
reactive
intermediates,
dictate
enantioselective
addition,
allow
full
complement
stereoisomeric
products
via
simple
catalyst
permutation.
successful
execution
dual-electrocatalytic
programmed
activation
provides
significant
conceptual
advantage
will
serve
as
useful
foundation
further
research
cooperative
stereocontrolled
transformations
diversity-oriented
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(21), P. 14864 - 14874
Published: May 16, 2024
The
exploitation
of
carbon
dioxide
(CO2)
as
a
sustainable,
plentiful,
and
harmless
C1
source
for
the
catalytic
synthesis
enantioenriched
carboxylic
acids
has
long
been
acknowledged
pivotal
task
in
synthetic
chemistry.
Herein,
we
present
current-driven
nickel-catalyzed
reductive
carboxylation
reaction
with
CO2
fixation,
facilitating
formation
C(sp3)–C(sp2)
bonds
by
circumventing
handling
moisture-sensitive
organometallic
reagents.
This
electroreductive
protocol
serves
practical
platform,
paving
way
propargylic
(up
to
98%
enantiomeric
excess)
from
racemic
carbonates
CO2.
efficacy
this
transformation
is
exemplified
its
successful
utilization
asymmetric
total
(S)-arundic
acid,
(R)-PIA,
(S)-chizhine
D,
(S)-cochlearin
G,
(S,S)-alexidine,
thereby
underscoring
potential
electrosynthesis
achieve
complex
molecular
architectures
sustainably.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 19, 2025
ConspectusIn
recent
years,
our
research
group
has
dedicated
significant
effort
to
the
field
of
asymmetric
organometallic
electrochemical
synthesis
(AOES),
which
integrates
electrochemistry
with
transition
metal
catalysis.
On
one
hand,
we
have
rationalized
that
compounds
can
serve
as
molecular
electrocatalysts
(mediators)
reduce
overpotentials
and
enhance
both
reactivity
selectivity
reactions.
other
conditions
for
catalysis
be
substantially
improved
through
electrochemistry,
enabling
precise
modulation
metal's
oxidation
state
by
controlling
potentials
regulating
electron
transfer
rate
via
current
adjustments.
This
synergistic
approach
addresses
key
challenges
inherent
in
traditional
catalysis,
particularly
those
related
use
redox-active
chemical
reagents.
Furthermore,
redox
conveniently
tuned
modifying
their
ligands,
thereby
governing
reaction
regioselectivity
stereoselectivity.
As
a
result,
AOES
emerged
powerful
promising
tool
chiral
compounds.In
this
Account,
summarize
contextualize
efforts
AOES.
Our
primary
strategy
involves
leveraging
controllability
potential
regulate
organometallics,
facilitating
desired
An
efficient
platform
was
established
under
mild
conditions,
significantly
reducing
reliance
on
been
systematically
categorized
into
three
sections
based
distinct
electrolysis
modes:
combined
anodic
oxidation,
cathodic
reduction,
paired
electrolysis.
In
each
section,
highlight
innovative
discoveries
tailored
unique
characteristics
respective
modes.In
many
transformations,
metal-catalyzed
reactions
involving
reagents
utilizing
exhibit
similar
reactivities.
However,
also
observed
notable
differences
certain
cases.
These
findings
include
following:
(1)
Enhanced
efficiency
synthesis:
instance,
Rh-catalyzed
enantioselective
functionalization
C–H
bonds
demonstrates
superior
efficiency.
(2)
Expanded
scope
transformations:
previously
challenging
achieved
due
tunability
potentials.
A
example
is
reductive
coupling
aryl
chlorides,
expands
range
accessible
transformations.
Additionally,
mechanistic
studies
explore
techniques
intrinsic
such
controlled
experiments,
impact
electrode
materials
catalyst
performance,
cyclic
voltammetry
studies.
investigations
provide
more
intuitive
understanding
behavior
catalysts
study
mechanisms,
guide
design
new
catalytic
systems.The
advancements
offer
robust
environmentally
friendly
sustainable
selective
By
integrating
developed
versatile
organic
not
only
enhances
but
reduces
environmental
impact.
We
anticipate
Account
will
stimulate
further
innovation
realm
AOES,
leading
discovery
systems
development
synthetic
methodologies.
