Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(22), P. 12313 - 12370
Published: Nov. 9, 2023
Late-stage
functionalization
(LSF)
introduces
functional
group
or
structural
modification
at
the
final
stage
of
synthesis
natural
products,
drugs,
and
complex
compounds.
It
is
anticipated
that
late-stage
would
improve
drug
discovery's
effectiveness
efficiency
hasten
creation
various
chemical
libraries.
Consequently,
products
a
productive
technique
to
produce
product
derivatives,
which
significantly
impacts
biology
development.
Carbon-carbon
bonds
make
up
fundamental
framework
organic
molecules.
Compared
with
carbon-carbon
bond
construction,
activation
can
directly
enable
molecular
editing
(deletion,
insertion,
atoms
groups
atoms)
provide
more
efficient
accurate
synthetic
strategy.
However,
selective
unstrained
still
one
most
challenging
projects
in
synthesis.
This
review
encompasses
strategies
employed
recent
years
for
cleavage
by
explicitly
focusing
on
their
applicability
functionalization.
expands
current
discourse
reactions
providing
comprehensive
overview
types
bonds.
includes
C-C(sp),
C-C(sp2),
C-C(sp3)
single
bonds;
double
triple
bonds,
focus
catalysis
transition
metals
organocatalysts.
Additionally,
specific
topics,
such
as
ring-opening
processes
involving
three-,
four-,
five-,
six-membered
rings,
are
discussed,
exemplar
applications
these
techniques
showcased
context
bioactive
molecules
discovery.
aims
shed
light
advancements
field
propose
potential
avenues
future
research
realm
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
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(11), P. 2093 - 2098
Published: March 11, 2022
Palladium-catalyzed
synthesis
of
3-acyl
and
-allyl
indoles
has
been
realized
by
merging
nucleophilic
cyclization
ortho-alkynylanilines
with
ring
opening
three-membered
rings
such
as
cyclopropenones
gem-difluorinated
cyclopropanes.
These
functionalized
were
obtained
in
moderate
to
high
yields
stereoselectivity
both
cases.
This
protocol
provides
an
alternative
method
toward
under
mild
redox-neutral
conditions.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(15), P. 8857 - 8867
Published: July 10, 2022
The
unique
properties
of
the
fluorine-containing
compounds
and
their
widespread
applications
raise
demand
for
dependable
synthetic
methods
on
precise
introduction
substituents
into
organic
molecules.
Herein,
a
site-divergent
fluoroallylation
olefins
that
can
incorporate
fluoroallyl
motif
different
alkenyl
C–H
sites
is
disclosed.
gem-Difluorinated
cyclopropanes
are
employed
as
sources
via
rhodium-catalyzed
C–C
bond
activation.
This
strategy
provide
two
regioisomeric
fluorinated
skipped
dienes
in
good
yields
with
excellent
site-selectivity.
resulting
products
serve
useful
building
blocks
to
access
various
molecules
isosteric
β,
γ-unsaturated
amides,
which
promising
be
exploited
medicinal
chemistry.
Mechanistic
studies
revealed
electronic
property
rhodium
catalysts
crucial
controllable
site-selectivity,
providing
more
insights
beyond
methodology
tuning
selectivity
metal
catalysts.
ChemCatChem,
Journal Year:
2022,
Volume and Issue:
14(24)
Published: Aug. 11, 2022
Abstract
gem
‐Difluorocyclopropanes
(F
2
CPs)
have
aroused
considerable
attention
not
only
from
the
structural
perspective
but
also
due
to
their
ability
participate
in
various
valuable
transformations.
This
Review
summarizes
advances
catalytic
ring‐opening
reactions
of
‐F
CPs,
especially
emphasizing
reactivities
and
applications
those
non‐activated
ones
under
transition‐metal
catalysis.
Their
achievements,
synthetic
limitations
are
discussed
with
aim
stimulate
enthusiasm
for
further
development.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: April 4, 2023
Defluorinative
manipulation
of
polyfluorinated
molecules
has
shown
great
promise
due
to
its
granting
synthetic
versatility
inert
C-F
bonds.
The
development
chemo-,
stereo-
and
regioselective
strategies
realize
highly
efficient
formation
either
the
linear/branched
or
E/Z
products
from
gem-difluorocyclopropanes
(gem-F2
CPs)
is
a
challenging
task.
Herein,
we
have
realized
palladium/NHC-catalyzed
fluoroallylation/annulation
hydrazones
with
gem-F2
CPs
that
incorporate
hydrazone
N2
moiety
into
products.
thermodynamically
unstable
fluorinated
E-allylation
aryl
ketone
were
obtained
for
first
time,
while
di-alkyl
yielded
monofluorinated
branched
selectivity
under
similar
reaction
conditions.
With
aldehyde
hydrazones,
two
kinds
pyrazoles
via
defluorinative
allylation/annulation
cascade,
in
which
different
carbon
atoms
could
be
incorporated
pyrazole
rings
regiospecifically.
DFT
calculations
revealed
divergent
was
kinetically
controlled
final
C-C
bond
proceeded
through
7-membered
TS.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Aug. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(8), P. 3095 - 3102
Published: Jan. 1, 2023
A
regiodivergent
electrochemical
defluorocarboxylation
of
gem
-difluorocyclopropanes
is
realized,
providing
access
to
branched
and
linear
carboxylated
monofluorinated
alkenes.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(17), P. 6733 - 6738
Published: Jan. 1, 2023
A
metal
free,
visible-light
driven
α-C(sp
3
)−H
gem-difluoroallylation
of
glycine
derivatives
with
CF
-alkenes
and
1,3-enynes
is
presented
under
redox-neutral
conditions
good
yields
excellent
functional
group
compatibility.
