ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(18), P. 12238 - 12268
Published: Sept. 1, 2023
Organofluorine
compounds
have
attracted
extensive
attention
in
various
industrial
fields
due
to
their
unique
chemical
and
physical
properties.
Despite
increasing
demand
a
wide
range
of
scientific
fields,
the
synthesis
organofluorine
still
faces
several
problems,
such
as
difficulties
handling
fluorinating
reagents
control
chemoselectivity.
Compared
with
formation
C–F
bonds,
activation
functionalization
carbon–fluorine
bonds
is
very
important
but
challenging
topic
synthetic
chemistry.
Due
properties
nickel,
Ni-catalyzed
defluorinative
cross-couplings
been
greatly
developed
past
few
decades
powerful
strategies
for
construction
fluorinated
organic
compounds.
This
Review
summarizes
advances
cross-coupling
aryl
fluorides,
gem-difluorovinyl
trifluoromethyl
Israel Journal of Chemistry,
Journal Year:
2019,
Volume and Issue:
60(3-4), P. 195 - 206
Published: Aug. 21, 2019
Abstract
Nickel
catalysts
have
recently
played
an
important
role
for
rapidly
and
reliably
converting
feedstock
chemicals
into
valuable
compounds
of
interest
both
pharmaceutical
academic
laboratories.
Herein,
we
summarize
the
recent
advances
on
ability
nickel
to
trigger
olefin
isomerization
via
“chain‐walking”,
causing
a
displacement
catalyst
throughout
alkyl
chain
while
opening
up
new
grounds
forging
C−C
C‐heteroatom
linkages
at
remote,
yet
unfunctionalized,
sp
3
C−H
bonds.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Jan. 27, 2021
Enantiomerically
pure
chiral
amines
and
related
amide
derivatives
are
privilege
motifs
in
many
pharmacologically
active
molecules.
In
comparison
to
the
well-established
hydroamination,
transition
metal-catalysed
asymmetric
hydrofunctionalization
of
enamines
provides
a
complementary
approach
for
their
construction.
Here
we
report
NiH-catalysed
enantio-
regioselective
reductive
hydroarylation
N-acyl
enamines,
allowing
practical
access
broad
range
structurally
diverse,
enantioenriched
benzylamines
under
mild,
operationally
simple
reaction
conditions.
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
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(10), P. 9127 - 9133
Published: Sept. 4, 2019
Enantioselective
Ni-catalyzed
reductive
aryl
monofluoroalkenylation
of
alkenes
between
bromides
and
gem-difluoroalkenes
has
been
developed.
The
reaction
proceeding
under
room
temperature
base-free
conditions
tolerates
a
wide
range
functional
groups
on
both
coupling
partners.
Various
synthetically
useful
oxindoles
containing
monofluoroalkenyl
substituent
are
obtained
in
good
yields
with
85%–95%
enantiomeric
excess.
In
addition,
the
synthetic
method
can
be
further
applied
to
late-stage
complex
biologically
active
compounds.
Israel Journal of Chemistry,
Journal Year:
2020,
Volume and Issue:
60(3-4), P. 313 - 339
Published: March 1, 2020
gem-Difluorinated
alkenes
are
readily
accessible
building
blocks
that
can
undergo
functionalization
to
provide
a
broad
spectrum
of
fluorinated
and
non-fluorinated
products.
Herein,
we
review
recent
(since
2017)
transition
metal-catalyzed
transformations
these
specialized
summarize
general
reactivity
patterns
reactions.
Many
reactions
net
C-F
bond
deliver
monofluorinated
These
typically
proceed
through
β-fluoro
alkylmetal
intermediates
eliminate
β-fluoride
monofluoroalkene
A
second
series
exploit
coinage
metal
fluorides
add
F-
the
gem-difluorinated
alkene,
further
delivers
trifluoromethyl-containing
In
stark
contrast,
few
in
"fluorine-retentive
processes"
difluoromethylene-based
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
56(72), P. 10442 - 10452
Published: Jan. 1, 2020
Three-component
difunctionalization
ofgem-difluoroalkenesviathe
generation
and
transformation
of
a
α-fluoroalkylated
carbanion,
carbon–metal
species,
radical,
carbocation
intermediate.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(48), P. 21530 - 21534
Published: Aug. 28, 2020
Abstract
A
highly
enantio‐
and
regioselective
hydroarylation
process
of
vinylarenes
with
aryl
halides
has
been
developed
using
a
NiH
catalyst
new
chiral
bis
imidazoline
ligand.
broad
range
structurally
diverse,
enantioenriched
1,1‐diarylalkanes,
structure
found
in
number
biologically
active
molecules,
have
obtained
excellent
yields
enantioselectivities
under
extremely
mild
conditions.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(8), P. 6987 - 6992
Published: July 5, 2019
An
effective
Cu-catalyzed
selective
formal
carboxylation
of
C–F
bonds
with
an
atmospheric
pressure
CO2
is
reported.
A
variety
gem-difluoroalkenes,
gem-difluorodienes,
and
α-trifluoro-methyl
alkenes
show
high
reactivity
selectivity
for
this
ipso
monocarboxylation.
Under
mild
conditions,
diverse
important
α-fluoroacrylic
acids
α,α-difluorocarboxylates
are
obtained
in
good-to-high
yields.
Moreover,
operationally
simple
protocol
features
good
functional
group
tolerance,
readily
scalable,
the
resulting
products
converted
into
bioactive
α-fluorinated
carbonyl
compounds,
indicating
potential
application
biochemistry
drug
discovery.
Mechanistic
studies
reveal
that
fluorinated
boronate
esters
might
be
vital
intermediates
transformation.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(13), P. 5398 - 5402
Published: Jan. 17, 2020
We
report
a
NiH-catalyzed
migratory
defluorinative
coupling
between
two
electronically
differentiated
olefins.
A
broad
range
of
unactivated
donor
olefins
can
be
joined
directly
to
acceptor
containing
an
electron-deficient
trifluoromethyl
substituent
in
both
intra-
and
intermolecular
fashion
form
gem-difluoroalkenes.
This
shows
site-
chemoselectivity
under
mild
conditions,
with
the
formation
tertiary
or
quaternary
carbon
center.
