Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(36)
Published: June 13, 2024
Abstract
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel‐catalyzed
system
that
facilitates
various
deuterium‐labeled
through
hydrodeuteroalkylation
d2‐labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
2
O
as
source
via
single‐step
pH‐dependent
hydrogen
isotope
exchange
(HIE).
Our
method
allows
for
high
incorporation,
offers
precise
control
over
site
insertion
within
an
chain.
This
technique
proves
to
be
invaluable
compounds,
especially
those
relevance.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 18892 - 18898
Published: July 5, 2024
Herein,
we
designed
a
reaction
for
the
desymmetrization-addition
of
cyclopropenes
to
imines
by
leveraging
synergy
between
photoredox
and
asymmetric
cobalt
catalysis.
This
protocol
facilitated
synthesis
series
chiral
functionalized
cyclopropanes
with
high
yield,
enantioselectivity,
diastereoselectivity
(44
examples,
up
93%
yield
>99%
ee).
A
possible
mechanism
involving
cyclopropene
desymmetrization
Co-H
species
imine
addition
Co-alkyl
was
proposed.
study
provides
novel
route
important
extends
frontier
metallaphotoredox
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 6, 2024
Abstract
General,
catalytic
and
enantioselective
construction
of
chiral
α,α
-dialkyl
indoles
represents
an
important
yet
challenging
objective
to
be
developed.
Herein
we
describe
a
cobalt
catalyzed
anti-
Markovnikov
alkene
hydroalkylation
via
the
remote
stereocontrol
for
synthesis
other
N
-heterocycles.
This
asymmetric
C(sp
3
)−C(sp
)
coupling
features
high
flexibility
in
introducing
diverse
set
alkyl
groups
at
α
-position
The
utility
this
methodology
has
been
demonstrated
by
late-stage
functionalization
drug
molecules,
bioactive
natural
products
functional
materials,
identification
class
molecules
exhibiting
anti-apoptosis
activities
UVB-irradiated
HaCaT
cells.
Ligands
play
vital
role
controlling
reaction
regioselectivity.
Changing
ligand
from
bi-dentate
L6
tridentate
L12
enables
CoH-catalyzed
hydroalkylation.
Mechanistic
studies
disclose
that
involves
migratory
insertion
process
while
MHAT
process.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(25), P. 17140 - 17149
Published: June 12, 2024
Enantioselective
three-component
difunctionalization
of
alkenes
with
boron
reagents
represents
an
attractive
strategy
for
assembling
three-dimensional
chiral
organoboron
compounds.
However,
regio-
and
enantiocontrol
comprise
the
pivot
challenges
in
these
transformations,
which
predominantly
require
use
activated
conjugated
alkenes.
Herein,
by
utilizing
various
carbonyl
directing
groups,
including
amides,
sulfinamides,
ketones,
esters,
we
succeed
realizing
a
nickel-catalyzed
1,2-borylalkynylation
unactivated
to
enable
simultaneous
incorporation
entity
sp-fragment
across
double
bond.
The
products
contain
boryl,
alkynyl,
functional
groups
orthogonal
synthetic
reactivities,
offering
three
handles
further
derivatization
access
valuable
intermediates.
utility
this
ligand-enabled
asymmetric
protocol
has
been
highlighted
through
late-stage
decoration
drug-relevant
molecules.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: June 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
16(1)
Published: Nov. 3, 2023
Abstract
Sp3‐hybridized
carbons‐rich
molecules
play
a
crucial
role
in
drug
discovery.
Cobalt‐catalyzed
hydroalkylation
of
alkenes
and
alkynes
is
an
efficient
method
to
synthesize
these
compounds.
These
reactions
exhibit
wide
range
applicability
high
tolerance
for
functional
groups,
utilizing
readily
available
instead
hyperactive
metallic
reagents.
Herein,
we
summarize
the
advancements
cobalt‐catalyzed
alkynes,
according
different
reaction
mechanisms.
We
present
detailed
discussion
scope
limitations,
plausible
mechanisms
opportunities
further
development.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4290 - 4317
Published: Jan. 1, 2024
Nickel-catalyzed
hydrofunctionalization
of
π-substrates
is
a
possibly
effective
method
to
synthesize
several
value-added
molecular
architectures.
This
review
covers
the
NiH
catalyzed
reactions
alkenes,
alkynes
and
allenes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: April 29, 2024
Abstract
Cyclic
sulfones
have
demonstrated
important
applications
in
drug
discovery.
However,
the
catalytic
and
enantioselective
synthesis
of
chiral
cyclic
remains
challenging.
Herein,
we
develop
nickel‐catalyzed
regiodivergent
hydroalkylation
sulfolenes
to
streamline
alkyl
sulfones.
The
method
has
broad
scope
high
functional
group
tolerance.
regioselectivity
can
be
controlled
by
ligands
only.
A
neutral
PYROX
ligand
favors
C3‐alkylation
whereas
an
anionic
BOX
C2‐alkylation.
This
control
is
kinetic
origin
as
C2‐bound
Ni
intermediates
are
always
thermodynamically
more
stable.
Reactivity
study
a
wide
range
relevant
reveal
I
/Ni
III
cycle
with
II
−H
species
resting
state.
regio‐
enantio‐determining
step
insertion
this
into
2‐sulfolene.
work
provides
efficient
for
class
organic
compounds
enhances
mechanistic
understanding
Ni‐catalyzed
stereoselective
hydroalkylation.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8888 - 8895
Published: Jan. 1, 2024
A
highly
efficient
method
achieves
precise
construction
of
alkyl
chiral
centers
at
remote
C3-positions
in
five-membered
S/O-heterocycles
via
cobalt-catalyzed
asymmetric
hydroalkylation
heterocyclic
alkenes.
