Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(33), P. 6176 - 6181
Published: Aug. 11, 2022
Herein,
we
report
an
effective
method
to
offer
chiral
gem-difluorinated
cyclopropanes
containing
all-carbon
quaternary
stereocenter
by
rhodium-catalyzed
stereoablative
kinetic
resolution.
The
activation
of
a
sterically
hindered
C–C
bond
through
oxidative
addition
with
rhodium
complex
is
proposed
as
the
enantiodetermining
step.
A
wide
range
can
be
obtained
excellent
ee
values
(ee
=
87%
>99.9%),
which
are
demonstrated
useful
fluorine-containing
building
blocks
series
postfunctionalizations.
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
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(19), P. 11960 - 11965
Published: Sept. 13, 2021
A
cross-electrophile
coupling
between
gem-difluorinated
cyclopropanes
and
2,2-difluorovinyl
tosylate
via
dual
Ni/Pd
cooperative
catalysis
under
mild
reaction
conditions
is
presented.
Various
structurally
unique
organofluorine
compounds
bearing
both
monofluoroalkene
gem-difluoroalkene
moieties
can
be
effectively
afforded
in
good
yields
with
a
high
(Z)-selectivity.
The
synthetic
utility
of
this
protocol
has
been
successfully
demonstrated
by
the
late-stage
modification
series
complex
bioactive
molecules.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(11), P. 6495 - 6505
Published: May 17, 2022
Controlling
the
selectivity
of
synthetically
useful
reactions
has
been
a
longstanding
objective
organic
chemistry.
We
report
regiodivergent
synthetic
protocol
allowing
access
to
diverse
fluorinated
1,5-dienes
through
Pd/NHC-catalyzed
ring-opening
allylation
gem-difluorocyclopropanes.
Density
functional
theory
(DFT)
calculations
on
regioselectivity-determining
transition
states
provided
critical
insight
into
design
NHC
ligand
for
switching
regioselectivity.
Consistent
with
DFT
predictions,
N-heterocyclic
carbene
(NHC)
ligands
bulky
ortho
substituents
favored
branched
allylation,
IHept
providing
>
20:1
branched/linear
less
hindered
such
as
IMes
thermodynamically
more
stable
linear
products.
were
able
carry
out
late-stage
modification
various
complex
molecules
using
this
protocol.
Our
ligand-controlled
approach
provides
efficient
regioisomeric
from
same
starting
materials
and
constitutes
valuable
addition
toolbox
diversity-oriented
synthesis.
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.
Synlett,
Journal Year:
2022,
Volume and Issue:
34(01), P. 1 - 13
Published: July 28, 2022
Abstract
As
a
special
class
of
cyclopropanes,
gem-difluorinated
cyclopropanes
have
many
fascinating
properties
as
result
the
gem-difluoro
substitution;
thus,
their
reactions
received
much
attention
from
synthetic
chemistry
community.
Recently,
gradually
emerged
type
novel
and
unique
fluorinated
allylic
synthon
in
cross-coupling
for
synthesis
monofluoroalkenes.
Herein,
we
briefly
summarize
recent
advances
transition-metal-catalyzed
cyclopropanes.
1
Introduction
2
Palladium-Catalyzed
Reactions
with
Linear
Selectivity
3
Branched
4
Other
Metal-Catalyzed
5
Conclusions
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.
