Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(25)
Published: April 22, 2023
Abstract
We
report
that
a
nickel
catalyst
system
with
modified
1,1′‐spirobiindane‐7,7′‐diol‐phosphoramidite
(SPINOL)
as
the
chiral
ligand
can
enable
coupling
of
tertiary
cyclobutenols
and
arylboroxines
in
an
enantioconvergent
manner,
providing
cyclobutenes
all‐carbon
quaternary
stereocenter
good
yields
(up
to
84
%
yield)
excellent
enantioselectivities
>99
ee).
Moreover,
catalytic
be
applied
kinetic
resolution
under
slightly
conditions,
giving
enantioenriched
s
factor
up
>200.
The
reaction
uses
free
hydroxyl
groups
leaving
group
without
additional
activation
while
strained
ring
remains
untouched.
Preliminary
mechanistic
studies
reveal
inherent
discrepant
reactivity
two
enantiomers
is
key
controllable
process.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(45), P. 20875 - 20883
Published: Oct. 31, 2022
We
report
the
first
palladium
hydride
enabled
hydroalkenylation
of
strained
molecules.
This
new
mild
protocol
proceeds
via
a
regio-
and
chemoselective
hydropalladation
step,
followed
by
photoinduced
radical
alkyl
Heck
reaction.
methodology
represents
reactivity
mode
for
molecules
opens
avenues
catalysis.
The
reaction
is
compatible
with
wide
range
functional
groups
can
be
applied
to
complex
structures,
delivering
diverse
array
highly
valuable
modifiable
alkenylated
cyclobutanes
cyclopropanes.
A
hydroalkenylation/diastereoselective
rearrangement
cascade
toward
cyclopentene
scaffold
has
also
been
demonstrated.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(32)
Published: June 20, 2023
Direct
synthesis
of
gem-difluorinated
carbocyclic
molecules
represents
a
longstanding
challenge
in
organic
chemistry.
Herein,
Rh-catalyzed
[3+2]
cycloaddition
reaction
between
readily
available
cyclopropanes
(gem-DFCPs)
and
internal
olefins
has
been
developed,
enabling
the
efficient
cyclopentanes
with
good
functional
group
compatibility,
excellent
regioselectivity
diastereoselectivity.
The
resulting
products
can
undergo
downstream
transformations
to
access
various
mono-fluorinated
cyclopentenes
cyclopentanes.
This
demonstrates
use
gem-DFCPs
as
type
"CF2
"
C3
synthon
for
under
transition
metal
catalysis,
which
provides
potential
strategy
synthesizing
other
molecules.
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.
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.
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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 6188 - 6193
Published: April 8, 2024
Enantioselective
reduction
of
cyclopropenyl
esters
and
ketones
to
optically
active
cyclopropanes
has
been
achieved
by
using
whole-cell-overexpressing
ene-reductases
(EREDs).
By
these
enzymes,
trans-cyclopropanes
were
isolated
in
good
yield
high
enantiomeric
excess.
A
wide
range
cyclopropane
obtained,
a
variety
substituent
patterns
on
the
cyclopropenes
tolerated.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(15), P. 2674 - 2679
Published: April 11, 2023
The
construction
of
all-carbon
quaternary
centers
in
small-ring
systems
is
important
but
challenging
organic
synthesis.
Herein,
by
taking
gem-difluorocyclopropyl
bromides
(DFCBs)
as
a
type
general
and
versatile
building
block,
we
developed
practical
method
for
gem-difluorinated
cyclopropanes
(DFCs).
reaction
relies
on
the
involvement
radical
intermediate,
which
can
couple
with
wide
range
nucleophiles
under
copper
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(25)
Published: April 22, 2023
We
report
that
a
nickel
catalyst
system
with
modified
1,1'-spirobiindane-7,7'-diol-phosphoramidite
(SPINOL)
as
the
chiral
ligand
can
enable
coupling
of
tertiary
cyclobutenols
and
arylboroxines
in
an
enantioconvergent
manner,
providing
cyclobutenes
all-carbon
quaternary
stereocenter
good
yields
(up
to
84
%
yield)
excellent
enantioselectivities
>99
ee).
Moreover,
catalytic
be
applied
kinetic
resolution
under
slightly
conditions,
giving
enantioenriched
s
factor
up
>200.
The
reaction
uses
free
hydroxyl
groups
leaving
group
without
additional
activation
while
strained
ring
remains
untouched.
Preliminary
mechanistic
studies
reveal
inherent
discrepant
reactivity
two
enantiomers
is
key
controllable
process.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1738 - 1743
Published: Feb. 17, 2024
Abstract
In
this
work,
we
reported
a
method
for
construction
of
difluorocyclopropanes
through
visible
light‐promoted
[1+2]
cycloaddition
reaction
aryl
diazo
esters
with
gem
‐difluoroalkenes.
The
proceeds
under
mild
conditions,
encompasses
wide
range
substrates
(36
examples),
exhibits
good
tolerance
to
various
substituents,
and
demonstrates
diastereoselectivity
>20:1.
Additionally,
antifungal
activity
evaluation
revealed
that
these
derivatives
exhibited
certain
activity,
the
EC
50
values
products
towards
Botrytis
cinerea
Rhizoctonia
solani
were
measured
be
1.51
1.36
μM,
respectively,
which
are
significantly
lower
than
those
commercial
fungicides
Hymexazol
Azoxystrobin.
This
work
not
only
provides
an
efficient
synthesis
difluorocyclopropanyl
derivatives,
but
reveals
their
potential
applications
in
fungicide
creation.
