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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 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.
Chemical Communications,
Год журнала:
2024,
Номер
60(28), С. 3764 - 3773
Опубликована: Янв. 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.
Chemical Communications,
Год журнала:
2021,
Номер
57(52), С. 6400 - 6403
Опубликована: Янв. 1, 2021
Cu/Pd-Catalyzed
borylfluoroallylation
of
alkenes
with
gem-difluorinated
cyclopropanes
and
B2pin2
was
achieved,
providing
a
modular
general
strategy
for
the
synthesis
monofluoroalkenes.
Synlett,
Год журнала:
2022,
Номер
34(01), С. 1 - 13
Опубликована: Июль 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
Chinese Journal of Chemistry,
Год журнала:
2022,
Номер
40(19), С. 2345 - 2355
Опубликована: Июнь 28, 2022
Comprehensive
Summary
Monofluoroalkenes
are
important
and
versatile
privileged
components
in
pharmacologically
relevant
molecules.
Here,
we
report
a
method
for
the
selective
construction
of
these
compounds
diversity‐oriented
fashion
through
regiodivergent
cross‐coupling
gem
‐difluorocyclopropanes
with
allylboronates
by
employing
palladium
catalyst
two
different
ligands,
which
were
used
as
allyl
electrophiles
C—C
C—F
bond
activation.
In
presence
2‐biphenylyl(diphenyl)phosphine
ligand,
linear‐selective
allyl–allyl
formation
is
highly
obtained,
while
utilizing
sterically
hindered
BrettPhos
(dicyclohexyl[3,6‐dimethoxy‐2',4',6'‐tris(1‐methylethyl)[1,1'‐biphenyl]‐2‐yl]phosphine)
ligand
favors
generation
branched‐selective
product.
Experimental
computational
studies
investigated
key
steps
reactions,
revealing
origin
ligand‐controlled
regiodivergence.
Organic Letters,
Год журнала:
2022,
Номер
24(28), С. 5051 - 5055
Опубликована: Июль 14, 2022
A
new
Co-catalyzed
sequential
C-C
and
C-F
activation
of
gem-difluorinated
cyclopropanes
(gem-FCPs)
to
form
nucleophilic
fluoroallylcobalt,
followed
by
addition
aldehydes,
is
reported.
The
protocol
features
the
regioselective
cleavage
dual
chemical
bonds
readily
available
gem-FCPs
prepare
easily
separable
linear
(Z)-
(E)-fluorinated
homoallylic
alcohols
with
a
broad
scope.
This
discovery
established
strategy
for
efficient
transformation
as
well
synthesis
challenging
fluorinated
alcohols.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(41)
Опубликована: Авг. 23, 2022
Reported
herein
is
the
efficient
synthesis
of
tetra-
and
tri-substituted
(Z)-fluoro-
(Z)-chloro-borylalkenes
by
Boron-Wittig
reaction
ketones
aldehydes
with
bench-top
stable
halo-diborylmethanes.
The
substrate
scope
broad
proceeds
from
a
diverse
range
including
biologically
relevant
molecules
fluoro-
or
chloro-diborylmethanes,
providing
in
good
yields
high
stereoselectivity.
utilities
obtained
are
highlighted
further
modifications
to
afford
fluoroalkene
derivatives
all-carbon
substituted
alkene.
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.
