Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis
ACS Catalysis,
Год журнала:
2024,
Номер
14(20), С. 15790 - 15798
Опубликована: Окт. 10, 2024
Here,
we
report
a
photoredox
and
nickel-catalyzed
cross-electrophile
coupling
strategy
for
the
asymmetric
three-component
1,2-alkylarylation
of
vinyl
boronates
with
(hetero)aryl
bromides
(2°,
3°)-alkyl
redox-active
esters
in
presence
Hantzsch
ester.
With
fluorinated
pyridyl-substituted
chiral
biimidazoline
ligand,
this
reaction
enables
straightforward
access
to
wide
variety
synthetically
valuable
α-aryl
from
readily
available
starting
materials.
This
features
mild
conditions,
broad
substrate
generality,
good
functional
group
tolerance
proceeds
without
using
metal
reductants
or
alkyl
halides.
Furthermore,
alkenyl
halides
other
electron-deficient
alkenes
such
as
acrylates
phosphonates
can
be
applied
successfully.
Preliminary
mechanistic
studies
shed
light
on
potential
pathways
roles
organic
amines.
Язык: Английский
Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
ConspectusElectrochemistry
has
been
used
as
a
tool
to
drive
chemical
reactions
for
more
than
two
centuries.
With
the
help
of
an
electrode
and
power
source,
chemists
are
provided
with
system
whose
potential
can
be
precisely
dialed
in.
The
theoretically
infinite
redox
range
renders
electrochemistry
capable
oxidizing
or
reducing
some
most
tenacious
compounds.
Indeed,
electroreduction
offers
alternative
generating
highly
active
intermediates
from
electrophiles
(e.g.,
halides,
alkenes,
etc.)
in
organic
synthesis,
which
untouchable
traditional
reduction
methods.
Meanwhile,
reductive
coupling
extensively
utilized
both
industrial
academic
settings
due
their
ability
swiftly,
accurately,
effectively
construct
C–C
C–X
bonds,
present
innovative
approaches
synthesizing
complex
molecules.
Nonetheless,
its
application
is
constrained
by
several
inherent
limitations:
(a)
requirement
stoichiometric
quantities
agents,
(b)
scarce
activation
strategies
inert
substrates
high
potentials,
(c)
incomplete
mechanistic
elucidation,
(d)
challenges
isolation
intermediates.
merging
represents
attractive
approach
address
above
limitations
synthesis
seen
increasing
use
synthetic
community
over
past
few
years.Since
2020,
our
group
dedicated
developing
electroreductive
cross-coupling
using
readily
available
small
molecules,
such
arenes,
CO2,
D2O,
value-added
products.
Electroreductive
chemistry
versatile
powerful
capacity
precise
selectivity
control,
allowed
us
develop
three
electrochemical
modes
lab:
(1)
An
economically
advantageous
direct
(EDR)
strategy
that
emphasizes
efficiency,
achieves
atom
utilization,
minimizes
unnecessary
atomic
waste.
(2)
A
class
organo-mediated
(EOMR)
methods
controlling
reaction
pathways.
This
allows
modulation
processes
enhance
efficiency
selectivity.
(3)
metal-catalyzed
(EMCR)
method
enables
selective
functionalization
specific
bonds
functional
groups
under
mild
conditions,
thereby
occurrence
side
reactions.
We
commenced
studies
establishing
organic-mediator-promoted
carboxylation
aryl
alkyl
halides.
was
then
employed
arylcarboxylation
simple
styrenes
halides
manner.
electrolysis
arenes
epoxides
CO2
carboxyl
source
achieved.
Moreover,
through
adjustment
we
successfully
accomplished
deuteration
olefins,
unactivated
enabling
efficient
formation
D-labeled
Finally,
building
on
previous
understanding
developed
series
alkylation
enable
C(sp3)–C(sp3)
Язык: Английский
Visible-Light-Induced photoredox aerobic coupling of sulfonium ylides and amines leading to E-selective formation of 2-amino-2-butene-1,4-diones
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
novel
visible-light-induced
photoredox
three-component
aerobic
coupling
reaction
of
sulfoxonium
ylides
and
amines
is
reported.
Язык: Английский
Recent Progress in Visible Light‐Mediated Synthesis of γ‐lactams
Helvetica Chimica Acta,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 30, 2025
Abstract
The
integration
of
sustainable
practices,
such
as
employing
renewable
light
sources
for
synthesizing
valuable
synthetic
scaffolds,
has
been
progressing
over
the
past
few
decades.
Among
these
noteworthy
organic
frameworks,
lactams,
particularly
γ‐lactams,
have
established
their
prominence
due
to
extensive
applications
in
pharmaceutical,
agricultural,
and
medicinal
domains.
This
growing
significance
γ‐lactams
spurred
considerable
interest
synthesis,
especially
via
milder,
more
sustainable,
environmentally
friendly
methods.
In
recent
years,
numerous
innovative
reaction
mechanisms
explored,
highlighting
how
photocatalysis
can
enable
formation
from
readily
accessible
precursors
through
C−N
bond
cyclization
processes.
review
emphasizes
potential
photocatalytic
strategies
not
only
enhance
current
methods
but
also
foster
development
greener
chemical
processes
future.
Язык: Английский
Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 5, 2025
Photoredox
catalysis
has
emerged
as
a
powerful
tool
for
forming
and
breaking
chemical
bonds,
further
taking
hold
with
its
integration
asymmetric
catalysis.
While
the
dual-catalytic
approach
led
to
successful
examples
of
control
stereogenic
centers,
axes
remained
underexplored.
In
this
study,
an
acylimine
intermediate
was
generated
through
photoredox
catalysis,
symmetric
substrate,
2-arylresorcinol,
desymmetrized
aid
chiral
phosphoric
acid
Using
approach,
center
axis
were
successfully
controlled
provide
natural-product-driven
compound.
The
origins
enantioselectivity
diastereoselectivity
investigated
density
functional
theory
study
four
possible
enantiodetermining
transition
states.
Consequently,
first
total
syntheses
ring-contracted
naphthylisoquinoline
alkaloid
ancistrobrevolines
A
B
accomplished
concisely.
This
provides
not
only
novel
methodology
strategy
synthesize
alkaloids
but
also
direction
advance
catalytic
research
synthesis
studies.
Язык: Английский
Enantioconvergent Cross-Electrophile Coupling of 2-Aryloxetanes with Aryl and Vinyl Halides, or Anhydrides
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 7578 - 7587
Опубликована: Апрель 22, 2025
Язык: Английский
A Unified Approach to Chiral α-Aryl Ketones and Aldehydes via Ni-Catalyzed Asymmetric Reductive Cross-Coupling
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 8, 2025
We
disclose
a
highly
enantioselective
protocol
for
the
facile
preparation
of
protected
tertiary
α-aryl
ketones
and
aldehydes,
enabled
by
chiral
Ni/Biox-catalyzed
reductive
coupling
readily
accessible
α-iodoacetals
-ketals
with
(hetero)aryl
halides.
The
generality
method
is
demonstrated
its
excellent
performance
across
broad
range
(hetero)cyclic
acyclic
carbonyl
scaffolds.
reaction
thought
to
proceed
through
unactivated
acetal/ketal
α-carbon
radicals,
overcoming
challenges
related
ancillary
steric
bulkiness
moieties
lack
stabilizing
directing
factors.
Experimental
density
functional
theory
(DFT)
studies
reveal
plausible
radical
chain
mechanism
elucidate
observed
enantioselectivity.
This
avoids
postreaction
epimerization
issue
often
encountered
in
unprotected
aldehydes.
Thus,
it
holds
great
promise
rapid
synthesis
wide
array
important
natural
products
drug
molecules
based
on
aldehydes
leveraging
earth-abundant
nickel
catalysts.
Язык: Английский
Visible‐Light Mediated Nickel‐Catalyzed Asymmetric Difunctionalizations of Alkenes
Han‐Tong Zhao,
Jia‐Ni Lin,
Wei Shu
и другие.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(67)
Опубликована: Авг. 13, 2024
Abstract
Difunctionalizations
of
alkenes
represent
one
the
most
straightforward
protocols
to
build
molecular
complexity
due
simultaneous
construction
two
vicinal
bonds
cross
π‐bond
alkenes.
It
is
extremely
attractive
yet
challenging
control
stereochemistry
outcome
this
event.
Over
past
years,
visible‐light
and
Ni‐catalyzed
asymmetric
difunctionalizations
provide
an
environmental
benign
promising
solution
for
saturated
carbon
centers
with
regio‐
enantioselectivity.
In
Concept,
initiative
progress
enantioselective
enabled
by
nickel
catalysis
has
been
summarized.
Moreover,
further
efforts
directions
development
mediated
discussed.
Язык: Английский