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
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4942 - 4957
Published: Feb. 7, 2024
Four-membered
carbocycles
are
fundamental
substructures
in
bioactive
molecules
and
approved
drugs
serve
as
irreplaceable
building
blocks
organic
synthesis.
However,
developing
efficient
protocols
furnishing
diversified
four-membered
ring
compounds
a
highly
regio-,
diastereo-,
enantioselective
fashion
remains
challenging
but
very
desirable.
Here,
we
report
the
unprecedented
asymmetric
transfer
hydrogenation
of
cyclobutenediones.
The
reaction
can
selectively
afford
three
types
products
high
yields
with
stereoselectivities,
functionalized
enable
series
further
transformations
to
form
more
compounds.
Asymmetric
synthesis
di-,
tri-,
tetrasubstituted
has
also
been
achieved.
Systematic
mechanistic
studies
theoretical
calculations
have
revealed
origin
regioselectivity,
key
transition
state
models,
sequence
double
triple
processes.
work
provides
new
choice
for
catalytic
cyclobutanes
related
structures
demonstrates
robustness
accurate
selectivity
control
substrates.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
The
utilization
of
high-valent
metal
catalysts
to
promote
cycloaddition
reactions
involving
π
bonds
through
C-C
bond
activation
remains
challenging.
Despite
extensive
research,
the
aldehydes
with
cyclopropenones
catalyzed
by
complexes
has
not
been
documented.
Herein,
we
disclose
a
novel
Rh(III)-catalyzed
reaction
between
and
aldehydes,
enabling
efficient
synthesis
highly
functionalized
furanones.
A
detailed
mechanistic
investigation
was
conducted,
revealing
likely
involvement
tripodal
Rh-carbene
intermediate
in
catalytic
cycle,
which
facilitates
product
release
pathway.
This
exhibits
broad
substrate
scope,
good
functional
group
compatibility,
high
atom
economy,
thereby
offering
versatile
general
approach
construction
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(4), P. 2234 - 2239
Published: Jan. 27, 2023
The
palladium-catalyzed
skeletal
rearrangement
of
3-arylcyclobutanones
into
1-indanones
is
reported.
A
Pd(0)/IMes
catalyst
allows
for
the
cleavage
C(carbonyl)–C(sp3)
and
C(sp2)–H
bonds
to
result
in
rearrangement,
neither
an
extra
reactive
functional
group
nor
a
directing
required
promote
reaction.
Deuterium-labeling
experiments
indicate
that
C–C
bond
initially
activated
subsequent
C–H
activation
involved
rate-determining
step.
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.
ChemistrySelect,
Journal Year:
2023,
Volume and Issue:
8(32)
Published: Aug. 23, 2023
Abstract
Cyclopropanols,
due
to
their
particular
chemistry,
can
participate
in
various
synthetic
reactions
with
retention
or
cleavage
of
the
strained
three‐membered
ring.
Direct
cross‐coupling
ring‐opening
reaction
such
molecules
access
organic
compounds,
as
ketones
has
great
importance
medicinal
chemistry
and
material
sciences.
Hence,
coupling
reaction/cyclization
cyclopropanols
for
constructing
new
valuable
presence
a
transition
metal
catalyst
under
metal‐free
conditions
is
described
this
context.
The
features
are
discussed,
mechanisms
challenging
highlighted.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 28, 2025
The
enantioselective
ring-opening
reactions
of
methylenecyclopropanes
(MCPs)
involving
C–C
bond
activation
via
oxidative
addition
transition
metals
have
been
rarely
reported.
Here,
we
disclose
a
Pd/Cu-catalyzed
enantio-
and
regioselective
coupling
between
cyclic
imino
esters
MCPs
to
produce
α-allylated
2H-pyrrole
derivatives.
In
this
reaction,
azomethine
ylide
formed
by
chiral
copper
catalyst
with
ketimine
ester
would
serve
as
nucleophile
react
activated
palladium
catalysis.
This
bimetallic
system
exhibited
broad
substrate
scope
high
regio-
enantioselectivities.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
A
novel
cascade
Pd-catalyzed
cross-coupling
reaction
of
cyclopropyl
alcohol-derived
ketone
homoenolate
with
2-Br-p-quinone
methides
and
2-Br-cinnamate
esters
followed
by
a
1,6-
1,4-conjugate
addition
is
disclosed.
This
protocol
converts
various
alcohols
into
homoenolate,
which
undergoes
C-C
bond
formation
2-Br
p-quinone
esters.
The
salient
features
this
methodology
include
its
operational
simplicity,
mild
conditions,
an
environmentally
benign
protocol,
high
efficiency,
good
to
excellent
yields,
wide
substrate
scope.
