Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
We
present
a
highly
efficient
and
versatile
nickel-catalyzed
protocol
for
the
reductive
cross-coupling
of
unactivated
CF2H-substituted
electrophiles
with
wide
variety
aryl
alkenyl
halides.
This
novel
approach
offers
high
catalytic
reactivity
broad
functional
group
compatibility,
enabling
late-stage
fluoroalkylation
drug
molecules.
Nature Catalysis,
Journal Year:
2024,
Volume and Issue:
7(6), P. 655 - 665
Published: April 29, 2024
Abstract
The
development
of
novel
strategies
to
rapidly
construct
complex
chiral
molecules
from
readily
available
feedstocks
is
a
long-term
pursuit
in
the
chemistry
community.
Radical-mediated
alkene
difunctionalizations
represent
an
excellent
platform
towards
this
goal.
However,
asymmetric
versions
remain
highly
challenging,
and
more
importantly,
examples
featuring
simple
hydrocarbons
as
reaction
partners
are
elusive.
Here
we
report
three-component
dicarbofunctionalization
capitalizing
on
direct
activation
C(
sp
3
)–H
bonds
through
combination
photocatalysed
hydrogen
atom
transfer
nickel
catalysis.
This
protocol
provides
efficient
for
installing
two
vicinal
carbon–carbon
across
alkenes
atom-economic
fashion,
providing
wide
array
high-value
α-aryl/alkenyl
carbonyls
phosphonates,
well
1,1-diarylalkanes
ubiquitous
alkane,
ether
alcohol
feedstocks.
method
exhibits
operational
simplicity,
broad
substrate
scope
regioselectivity,
chemoselectivity
enantioselectivity.
compatibility
with
bioactive
motifs
expedient
synthesis
pharmaceutically
relevant
highlight
synthetic
potential
protocol.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 17, 2024
Abstract
Transition
metal-catalyzed
reductive
difunctionalization
of
alkenes
with
alkyl
halides
is
a
powerful
method
for
upgrading
commodity
chemicals
into
densely
functionalized
molecules.
However,
super
stoichiometric
amounts
metal
reductant
and
the
requirement
installing
directing
group
to
suppress
inherent
β-H
elimination
bring
great
limitations
this
type
reaction.
We
demonstrate
herein
that
two
different
accessible
via
radical-anion
relay
Na
2
S
O
4
as
both
sulfone-source.
The
together
electron-shuttle
catalyst
crucial
divert
mechanistic
pathway
toward
formation
sulfone
anion
instead
previously
reported
alkylmetal
intermediates.
Mechanistic
studies
allow
identification
carbon-centered
radical
sulfur-centered
radical,
which
are
in
equilibrium
capture
or
extrusion
SO
could
be
converted
accelerated
by
iron
catalysis,
leading
observed
high
chemoselectivity.
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
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(13)
Published: Jan. 31, 2023
Transition-metal
catalyzed
intermolecular
1,2-diarylation
of
electronically
unactivated
alkenes
has
emerged
as
an
extensive
research
topic
in
organic
synthesis.
However,
most
examples
are
mainly
limited
to
terminal
alkenes.
Furthermore,
transition-metal
asymmetric
still
remains
unsolved
and
is
a
formidable
challenge.
Herein,
we
describe
highly
efficient
directed
nickel-catalyzed
reductive
internal
with
high
diastereoselectivities.
More
importantly,
our
further
effort
towards
enantioselective
the
challenging
achieved,
furnishing
various
polyarylalkanes
featuring
benzylic
stereocenters
yields
good
enantioselectivities
Interestingly,
generation
cationic
Ni-catalyst
by
adding
alkali
metal
fluoride
key
increased
efficiency
this
reaction.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 1, 2024
Comprehensive
Summary
Organofluorine
compounds
have
attracted
substantial
interest
in
life
and
materials
sciences
due
to
the
unique
properties
of
fluorine
atom(s)
that
often
change
physicochemical
biological
organic
molecules.
Transition‐metal‐mediated
cross‐electrophile
coupling
between
carbon
electrophiles
fluoroalkyl
has
emerged
as
a
straightforward
efficient
route
for
synthesis
wide
range
fluoroalkylated
because
its
synthetic
convenience
without
tedious
organometallic
reagents.
Moreover,
alkenes
or
alkynes‐involved
three‐component
couplings
provide
rapid
effective
access
carbonfunctionalized
alkanes
alkenes.
Herein,
we
comprehensively
summarize
transition‐metal‐mediated
reductive
fluoroalkylation
diverse
through
historical
perspective,
including
trifluoromethylation,
difluoroalkylation,
monofluoroalkylation,
so
on.
Different
transition
metals
(Cu,
Ni,
etc
.)
strategies
are
discussed,
which
nickel‐catalyzed
reactions
represent
an
attractive
site‐selectively
organofluorine
compounds.
Key
Scientists
As
early
1965,
McLoughlin
Thrower
finished
first
stoichiometric
copper‐mediated
aromatic
iodides
with
iodides.
However,
excess
elevated
temperature
were
used
this
method.
In
1969,
Kobayashi
Kumadaki
reported
studies
on
trifluoromethylation
halides
trifluoromethyl
iodide.
After
more
than
four
decades,
Zhang
group
developed
β
‐fluorinated
alkylation
(hetero)aryl
secondary
alkyl
bromides
2015,
difluoromethylation
chlorides
chlorodifluoromethane
ClCF
2
H
2017.
The
also
enantioselective
alkyl‐arylation
3,3,3‐trifluoropropene
tertiary
2018,
MacMillan
novel
copper/photoredox
dual
catalytic
system
aryl
(
S
)‐(trifluoromethyl)
dimesitylsulfonium
triflate
presence
tris‐(trimethylsilyl)
silanol.
They
nickel/photoredox
catalyzed
silane.
During
time,
Wang
monofluoroalkylation
monofluoroalkyl
halides.
From
2021
2023,
same
further
series
trifluoroalkylation
aryl,
alkenyl,
acyl
nonfluorinated
alkynes
could
be
couplings.
Chu
fluoroalkyl‐acylation
Later,
they
fluoroalkyl‐arylation
unactivated
tethering
pendant
chelating
group.
2019,
Chaładaj
palladium‐catalyzed
perfluoroalkyl‐arylation
perfluoroalkyl
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(2), P. 1667 - 1676
Published: Jan. 7, 2025
We
report
a
Ni-catalyzed
vicinal
alkylarylation
of
unactivated
alkenes
in
γ,δ-
and
δ,ε-alkenylamines
with
aryl
halides
alkylzinc
reagents.
The
reaction
is
enabled
by
amine
coordination
can
use
all
primary,
secondary,
tertiary
amines.
constructs
two
new
C(sp3)-C(sp3)
C(sp3)-C(sp2)
bonds
produces
δ-
ε-arylamines
C(sp3)-branching
at
the
γ-
δ-positions.
A
variety
heteroaryl
iodides
both
primary
secondary
reagents
be
used
as
coupling
carbon
sources.
Mechanistic
studies
suggest
that
cooperative
effect
organic
nitriles
electron-deficient
(EDAs)
ligands.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(18)
Published: Aug. 3, 2023
Abstract
Asymmetric
multicomponent
reactions
are
considered
as
efficient
protocols
for
constructing
complex
chiral
molecules
because
of
their
step‐
and
atom‐economy.
Nickel‐catalyzed
asymmetric
three‐component
dicarbofunctionalization
alkenes
has
been
well
developed
in
recent
years,
which
is
used
the
area
total
synthesis
natural
products
late‐stage
modification
drugs
rapid
incorporation
sp
3
‐enriched
carbon
centers.
In
this
concept,
significant
breakthroughs
field
summarized,
together
with
related
mechanisms.
Moreover,
remaining
challenges
potential
opportunities
also
highlighted.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Jan. 19, 2024
Abstract
In
modern
organic
chemistry,
harnessing
the
power
of
multicomponent
radical
reactions
presents
both
significant
challenges
and
extraordinary
potential.
This
article
delves
into
this
scientific
frontier
by
addressing
critical
issue
controlling
selectivity
in
such
complex
processes.
We
introduce
a
novel
approach
that
revolves
around
reversible
addition
thiyl
radicals
to
multiple
bonds,
reshaping
landscape
reactions.
The
key
lies
intricate
interplay
between
reversibility
energy
landscapes
governing
C−C
bond
formation
thiol‐yne‐ene
developed
not
only
allows
prioritize
cascade,
dominating
over
alternative
reactions,
but
also
extends
scope
coupling
products
obtained
from
alkenes
alkynes
various
structures
electron
density
distributions,
regardless
their
relative
polarity
difference,
opening
doors
more
versatile
synthetic
possibilities.
present
study,
we
provide
powerful
tool
for
atom‐economical
C−S
formation,
paving
way
efficient
synthesis
molecules.
Carrying
out
our
experimental
computational
studies,
elucidated
fundamental
mechanisms
underlying
cascades,
knowledge
can
be
broadly
applied
field
chemistry.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: April 15, 2024
Due
to
the
unique
effect
of
fluorine
atoms,
efficient
construction
high-value
alkyl
fluorides
has
attracted
significant
interest
in
modern
drug
development.
However,
enantioselective
catalytic
strategies
for
assembly
highly
functionalized
chiral
C(sp