Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(8), С. 823 - 828
Опубликована: Дек. 8, 2023
Comprehensive
Summary
Herein,
we
report
nickel‐catalyzed
cross‐coupling
of
gem
‐difluorinated
cyclopropanes
with
boronic
acids,
providing
the
corresponding
arylated
2‐fluoroallylic
scaffolds.
This
approach
used
commercially
available
phosphine
ligand
Xantphos
to
obtain
monofluorinated
alkenes
high
regioselectivity
and
Z
‐stereoselectivity.
Mechanistic
studies
proposed
a
Ni(II)‐fluoroallyl
pathway
excluded
radical
pathway.
Meanwhile,
DFT
study
reductive
elimination
clarified
origin
linear
selectivity.
Chemical Science,
Год журнала:
2022,
Номер
13(42), С. 12419 - 12425
Опубликована: Янв. 1, 2022
The
control
of
linear/branched
selectivity
is
one
the
major
focuses
in
transition-metal
catalyzed
allyl-allyl
cross-coupling
reactions,
which
bond
connection
occurs
at
terminal
site
both
allyl
fragments
forming
different
types
1,5-dienes.
Herein,
terminal/internal
regioselectivity
investigated
and
found
to
be
switchable
reactions
between
gem-difluorinated
cyclopropanes
allylboronates.
controlled
arises
from
fine-tuning
rhodium
catalytic
system.
Fluorinated
1,3-dienes,
1,4-dienes
1,5-dienes
are
therefore
produced
good
yields
with
respectively
isomerized
terminal,
internal,
regioselectivity.
Organic Letters,
Год журнала:
2023,
Номер
25(28), С. 5220 - 5225
Опубликована: Июль 12, 2023
An
efficient
palladium-catalyzed
2-fluoroallylation
of
P(O)H
compounds
with
gem-difluorocyclopropanes
is
presented.
The
reaction
provides
a
variety
2-fluoroallylic
phosphorus
in
good
yields
high
Z
selectivity
through
the
sequential
C-C
bond
activation,
C-F
cleavage,
and
C-P
coupling
process.
Various
H-phosphonates,
H-phosphinates,
secondary
phosphine
oxides
are
all
tolerated.
In
addition,
gram-scale
synthesis
late-stage
modification
complex
bioactive
molecules
show
practical
utilities
transformation.
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.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
22(1), С. 37 - 54
Опубликована: Ноя. 27, 2023
Developing
efficient
and
straightforward
strategies
to
rapidly
construct
structurally
distinct
diverse
organic
molecules
is
one
of
the
most
fundamental
tasks
in
synthesis,
drug
discovery
materials
science.
In
recent
years,
divergent
synthesis
functional
from
same
starting
has
attracted
significant
attention
been
recognized
as
an
powerful
strategy.
To
achieve
this
objective,
proper
adjustment
reaction
conditions,
such
catalysts,
solvents,
ligands,
etc.,
required.
review,
we
summarized
efforts
chemo-,
regio-
stereodivergent
reactions
involving
acyclic
cyclic
systems
catalyzed
by
palladium
complexes.
Meanwhile,
types,
including
carbonylative
reactions,
coupling
cycloaddition
well
probable
mechanism
have
also
highlighted
detail.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 9020 - 9024
Опубликована: Дек. 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.
Chemical Science,
Год журнала:
2024,
Номер
15(34), С. 13800 - 13806
Опубликована: Янв. 1, 2024
Metathesis
reactions
have
been
established
as
a
powerful
tool
in
organic
synthesis.
While
great
advances
were
achieved
double-bond
metathesis,
like
olefin
metathesis
and
carbonyl
single-bond
has
received
less
attention
the
past
decade.
Herein,
we
describe
first
C(sp
Organic Letters,
Год журнала:
2022,
Номер
24(45), С. 8429 - 8434
Опубликована: Ноя. 4, 2022
gem-Difluorinated
cyclopropanes
have
attracted
wide
research
interest
in
organic
synthesis
due
to
their
high
reactivity.
Herein,
we
report
a
Lewis
acid-catalyzed
cross-coupling
reaction
of
mono-
and
disubstituted
gem-difluorinated
with
nucleophiles.
The
formation
fluoroallyl
cation
species
triggered
via
the
acid-assisted
activation
C-F
bond
is
proposed
this
transformation.
then
trapped
by
nucleophiles,
including
electron-rich
arenes
allylsilanes,
deliver
series
fluoroallylic
products
good
yields.
provides
an
alternative
mode
for
using
as
surrogates.
Organic Letters,
Год журнала:
2022,
Номер
24(33), С. 6176 - 6181
Опубликована: Авг. 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.
