Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(11)
Published: Jan. 10, 2024
Abstract
Here
we
present
a
modular,
chemo‐,
regio‐,
and
stereoselective
synthesis
of
fully‐substituted
configuration‐defined
alkyl
vinyl
ethers
(AVEs)
using
simple
chemical
feedstocks.
The
distinctive
approach
involves
the
chemo‐
regioselective
functionalization
CF
2
unit
in
gem
‐difluorinated
cyclopropanes
with
O−H
C−H
nucleophiles
specific
order.
resulting
highly
functionalized
cyclopropanyl
then
undergo
ring‐opening
process
to
produce
AVEs.
These
AVEs
are
rarely
accessible
through
conventional
methods
easily
transformable.
Mechanistic
experiments
indicate
that
success
this
method
relies
on
use
dual‐functional
copper
catalysis,
which
is
involved
both
subsequent
process.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 22, 2024
Abstract
The
use
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
as
fluoroallyl
surrogates
under
transition‐metal
catalysis
has
drawn
considerable
attention
recently
but
such
reactions
are
restricted
to
producing
achiral
or
racemic
mono‐fluoroalkenes.
Herein,
we
report
the
first
enantioselective
allylation
indoles
rhodium
with
‐DFCPs.
This
reaction
shows
exceptional
branched
regioselectivity
towards
‐DFCPs,
which
provides
an
efficient
route
enantioenriched
fluoroallylated
wide
substrate
scope
and
good
functional
group
tolerance.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(11)
Published: Jan. 10, 2024
Here
we
present
a
modular,
chemo-,
regio-,
and
stereoselective
synthesis
of
fully-substituted
configuration-defined
alkyl
vinyl
ethers
(AVEs)
using
simple
chemical
feedstocks.
The
distinctive
approach
involves
the
chemo-
regioselective
functionalization
CF
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(28), P. 3764 - 3773
Published: Jan. 1, 2024
This
feature
article
summarizes
our
efforts
towards
developing
Rh-catalyzed
reactions
of
gem
-difluorinated
cyclopropanes,
briefly
discussing
the
design,
selectivity,
mechanisms
and
future
research
prospects.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: Feb. 27, 2024
A
novel
enantioselective
Tsuji-Trost-type
cross
coupling
reaction
between
gem-difluorinated
cyclopropanes
and
N-unprotected
amino
acid
esters
enabled
by
synergistic
Pd/Ni/chiral
aldehyde
catalysis
is
presented
herein.
This
transformation
streamlined
the
diversity-oriented
synthesis
(DOS)
of
optically
active
α-quaternary
α-amino
bearing
a
linear
2-fluoroallylic
motif,
which
served
as
an
appealing
platform
for
construction
other
valuable
enantioenriched
compounds.
The
key
intermediates
were
confirmed
HRMS
detection,
while
DFT
calculations
revealed
that
excellent
enantioselectivity
was
attributed
to
stabilizing
non-covalent
interactions
Pd(II)-π-fluoroallyl
species
Ni(II)-Schiff
base
complex.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 21, 2024
Abstract
Transition-metal
catalyzed
allylic
substitution
reactions
of
alkenes
are
among
the
most
efficient
methods
for
synthesizing
diene
compounds,
driven
by
inherent
preference
an
inner-sphere
mechanism.
Here,
we
present
a
demonstration
outer-sphere
mechanism
in
Rh-catalyzed
reaction
simple
using
gem
-difluorinated
cyclopropanes
as
allyl
surrogates.
This
unconventional
offers
opportunity
fluorine
recycling
via
C
−
F
bond
cleavage/reformation,
ultimately
delivering
carbofluorination
products.
The
developed
method
tolerates
wide
range
alkenes,
providing
access
to
secondary,
tertiary
fluorides
and
-difluorides
with
100%
atom
economy.
DFT
calculations
reveal
that
formation
goes
through
unusual
nucleophilic
allyl-Rh
species
instead
migration
insertion,
generated
carbon
cation
then
forms
tetrafluoroborate
fluoride
shuttle.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
The
transition-metal-catalyzed
ring-opening
functionalization
of
aziridines
presents
a
promising
approach
for
synthesizing
structurally
complex
amines.
However,
the
rearranged
poses
significant
challenges.
Herein,
we
report
first
alkenylation
with
aryl
alkenes
via
Ni-Brønsted
acid
co-catalysis,
leading
to
rapid
synthesis
diverse
array
allylamines
yields
reaching
up
91%.
Mechanistic
studies
suggest
that
reaction
occurs
through
rearrangement
aziridine
generate
an
imine
intermediate.
This
intermediate
is
subsequently
captured
by
alkene
under
nickel
catalysis,
ultimately
formation
allylamines.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(50), P. 9020 - 9024
Published: Dec. 8, 2023
This
study
presents
a
novel
method
for
the
regioselective
coupling
of
gem-difluorinated
cyclopropanes
with
gem-diborylmethane,
utilizing
Pd-catalyst
system.
innovative
approach
enables
synthesis
2-fluoroalkenyl
monoboronate
scaffolds
high
Z-selectivity.
The
resulting
products
undergo
further
transformations,
including
oxidation,
Suzuki
cross-coupling,
and
trifluoroborylation,
all
which
are
achieved
good
yields.
work
introduces
valuable
synthetic
pathway
to
access
important
fluorinated
compounds
various
applications
in
organic
chemistry.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(20)
Published: Jan. 25, 2024
C-F
Insertion
reactions,
where
an
organic
fragment
formally
inserts
into
a
carbon-fluorine
bond
in
substrate,
are
highly
attractive,
yet
largely
unexplored,
methods
to
prepare
valuable
fluorinated
molecules.
The
inherent
strength
of
bonds
and
the
resulting
need
for
large
thermodynamic
driving
force
initiate
cleavage
often
leads
sequestering
released
fluoride
unreactive
by-product.
Recently,
however,
several
groups
have
succeeded
overcoming
this
challenge,
opening
up
study
insertion
as
efficient
atom-economical
approach
compounds.
In
article,
recent
breakthroughs
discussed
focusing
on
key
conceptual
advances
that
allowed
both
subsequent
incorporation
product.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(18)
Published: March 9, 2024
Abstract
Transition‐metal
(TM)
catalyzed
reaction
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
has
drawn
much
attention
recently.
The
generally
occurs
via
the
activation
distal
C─C
bond
in
‐DFCPs
by
a
low‐valent
TM
through
oxidative
addition,
eventually
producing
mono‐fluoro
olefins
as
coupling
products.
However,
achieving
regioselective
proximal
that
overcomes
intrinsic
reactivity
catalysis
remains
elusive.
Here,
new
mode
enabled
high‐valent
copper
catalysis,
which
allows
exclusive
congested
is
presented.
achieves
fluoroarylation
uses
NFSI
(N‐fluorobenzenesulfonimide)
electrophilic
fluoro
reagent
and
arenes
C─H
nucleophiles,
enabling
synthesis
diverse
CF
3
‐containing
scaffolds.
It
proposed
species
plays
an
important
role
possibly
σ‐bond
metathesis.
