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.
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.
Synlett,
Journal Year:
2022,
Volume and Issue:
34(01), P. 1 - 13
Published: July 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
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(28), P. 5051 - 5055
Published: July 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.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(42), P. 12419 - 12425
Published: Jan. 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.
ACS Central Science,
Journal Year:
2023,
Volume and Issue:
9(2), P. 159 - 165
Published: Jan. 18, 2023
Lignin-derived
aromatic
chemicals
offer
a
compelling
alternative
to
petrochemical
feedstocks,
and
new
applications
are
the
focus
of
extensive
interest.
4-Hydroxybenzoic
acid
(H),
vanillic
(G),
syringic
(S)
readily
obtained
via
oxidative
depolymerization
hardwood
lignin
substrates.
Here,
we
explore
use
these
compounds
access
biaryl
dicarboxylate
esters
that
represent
biobased,
less
toxic
alternatives
phthalate
plasticizers.
Chemical
electrochemical
methods
developed
for
catalytic
reductive
coupling
sulfonate
derivatives
H,
G,
S
all
possible
homo-
cross-coupling
products.
A
conventional
NiCl2/bipyridine
catalyst
is
able
H-H
G-G
products,
but
catalysts
identified
afford
more
challenging
including
NiCl2/bisphosphine
S-S
NiCl2/phenanthroline/PdCl2/phosphine
cocatalyst
system
H-G,
H-S,
G-S.
High-throughput
experimentation
with
chemical
reductant
(Zn
powder)
shown
provide
an
efficient
screening
platform
identification
catalysts,
while
can
improved
yields
and/or
facilitate
implementation
on
larger
scale.
Plasticizer
tests
performed
poly(vinyl
chloride),
using
4,4'-biaryl
The
H-G
derivatives,
in
particular,
exhibit
performance
advantages
relative
established
petroleum-based
ester
plasticizer.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(28), P. 5220 - 5225
Published: July 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.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(20), P. 3647 - 3651
Published: May 17, 2022
Compared
with
conventional
reductive
coupling,
coupling
under
electrochemical
conditions
without
external
reductants
is
greener,
milder,
and
more
efficient
of
increasing
interest
to
organic
chemists.
In
this
work,
we
report
the
sacrificial
anode,
nickel-catalyzed
allylation
reaction
aryl
alkyl
halides.
The
can
be
applied
a
range
reagents
such
as
trifluoroalkenes,
oxalates,
acetates.
