Abstract
Catalytic
C(sp3)–H
cross-coupling
offers
an
attractive
strategy
for
constructing
C(sp3)-rich
complex
molecules
from
simple
feedstock
chemicals.
However,
simultaneously
controlling
chemo-
and
enantioselectivity
in
these
transformations,
particularly
C(sp3)–C(sp3)
bond
formation,
remains
a
formidable
challenge.
To
address
this
longstanding
challenge,
we
have
recently
developed
general
leveraging
nickel
photoredox
catalysis
to
achieve
various
enantioselective
reactions,
including
acylation,
alkenylation,
arylation,
(trideutero)methylation,
alkylation.
Our
approaches
exploit
photocatalytically
generated
bromine
radicals
hydrogen
atom
transfer,
converting
common
hydrocarbons
into
carbon-centered
radicals.
These
are
then
enantioselectively
coupled
with
diverse
electrophiles
the
presence
of
suitable
chiral
catalyst.
methods
open
new
avenues
cross-coupling,
offering
broad
substrate
scope,
high
functional
group
tolerance,
potential
late-stage
diversification
molecules.
holds
great
promise
unlocking
previously
elusive
chemical
space,
significant
implications
drug
discovery
development.
1
Introduction
2
Enantioselective
C(sp3)–C(sp2)
Cross-Couplings
3
4
Conclusions
Outlook
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 19, 2025
Radical-radical
cross-coupling
(RCC)
offers
a
promising
approach
for
carbon-carbon
bond
formation
in
organic
synthesis,
particularly
creating
complex,
three-dimensional
molecules.
However,
achieving
both
cross-
and
enantioselectivity
RCC
reactions
has
remained
significant
challenge.
Here,
we
report
novel
metallaphotoredox
platform
that
enables
highly
enantioselective
decarboxylative
coupling
of
carboxylic
acid
derivatives
with
aldehydes.
Our
strategy
leverages
independent
control
over
radical
generation
subsequent
through
fine-tuning
common
photocatalyst
simple
chiral
bis(oxazoline)
nickel
catalyst.
This
redox-neutral
protocol
requires
no
exogenous
oxidants
or
reductants
demonstrates
broad
substrate
scope
functional
group
compatibility
the
synthesis
enantioenriched
α-aryl
α-amino
ketones.
The
ketone
products
can
be
readily
transformed
into
valuable
β-amino
alcohols,
streamlining
access
to
these
important
motifs.
Furthermore,
showcase
potential
this
more
challenging
C(sp3)-C(sp3)
alkyl-alkyl
reactions.
unified
alkyl-acyl
represents
advance
asymmetric
catalysis
underscores
exploit
new
mechanisms
solve
long-standing
synthetic
problems.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5278 - 5305
Опубликована: Янв. 1, 2024
This
review
summarizes
the
latest
methodological
advances
in
photocatalytic
C(sp
3
)–H
functionalization,
with
a
particular
emphasis
on
formation
of
C–P,
C–B,
C–S
bonds,
etc
.,
and
some
prominent
efforts
asymmetric
C–H
functionalization.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13347 - 13355
Опубликована: Май 6, 2024
Azide
compounds
are
widely
present
in
natural
products
and
drug
molecules,
their
easy-to-transform
characteristics
make
them
used
the
field
of
organic
synthesis.
The
merging
transition-metal
catalysis
with
radical
chemistry
offers
a
versatile
platform
for
carboazidation
alkenes,
allowing
rapid
assembly
highly
functionalized
azides.
However,
direct
use
readily
available
hydrocarbon
feedstocks
as
sp
Green Chemistry,
Год журнала:
2024,
Номер
26(10), С. 5824 - 5831
Опубликована: Янв. 1, 2024
An
electrochemical
oxidation-induced
amination
of
simple
alkylarenes
with
sulfoximines
as
a
nitrogen
source
and
5,6-dimethyl-1
H
-benzo[
d
]imidazole
catalyst
was
developed.
The
hydrocarbamoylation
of
alkenes
with
isocyanates
is
a
promising
method
for
synthesizing
amides.
However,
applying
this
strategy
to
more
inert,
simple
alkenes,
such
as
styrenes,
α-olefins,
and
internal
poses
significant
challenges.
Here,
we
report
the
first
nickel-catalyzed
isocyanates,
facilitated
by
triethoxysilane
reduce
nickelacycle
intermediates.
By
switching
ligands─including
6,6′-dimethyl-2,2′-bipyridine
N-heterocyclic
carbene─this
efficiently
produces
amides
from
diverse
array
including
gaseous
olefins.
Chemical Science,
Год журнала:
2024,
Номер
15(31), С. 12511 - 12516
Опубликована: Янв. 1, 2024
We
report
a
site-
and
stereoselective
benzylic
C(sp
3
)–H
alkenylation
utilizing
metallaphotoredox
catalysis.
In
addition,
enantioselective
can
successfully
produce
highly
enantioenriched
tetrasubstituted
olefins.
ACS Catalysis,
Год журнала:
2024,
Номер
14(18), С. 13860 - 13866
Опубликована: Сен. 3, 2024
The
synthesis
of
axially
chiral
biaryls
continues
to
garner
significant
attention
in
the
scientific
community.
In
this
work,
we
introduce
a
Ni-catalyzed
desymmetrization
strategy
for
prochiral
dibromoarenes,
conducted
under
mild
reaction
conditions
and
with
good
functional
group
tolerance.
This
method
allows
from
readily
available
coupling
partners,
such
as
aldehydes,
ethers,
unactivated
alkyl
bromides.
Moreover,
has
been
successfully
applied
concise
enantioenriched
azulene-embedded
[7]helicene,
promising
organic
optoelectronics
material.
