Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(8), P. 2994 - 2999
Published: April 5, 2021
A
novel
diethylzinc-mediated
radical
1,2-addition
of
perfluoroalkyl
iodides
to
unactivated
alkenes
and
alkynes
is
presented,
which
demonstrates
a
way
generate
an
ethyl
difluoroacetate
radical.
This
method
highly
efficient
gives
full
conversions
the
substrates,
high
yields
products,
negligible
byproducts
requires
no
column
chromatography
purifications.
The
mild
conditions
enable
this
protocol
exhibit
excellent
functional
group
compatibility.
ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
8(8), P. 7287 - 7307
Published: June 25, 2018
Recent
protocols
and
reactions
for
catalytic
radical
perfluoroalkylations
will
be
described.
The
production
of
perfluoroalkyl
radicals
(RF
=
CnF2n+1,
n
≥
2),
which
effect
both
addition
substitution
on
organic
substrates,
can
realized
through
a
range
diverse
methods
such
as
the
well-established
visible-light
transition-metal-mediated
photocatalysis,
organic-dye-photocatalyzed
reactions,
electron
donor–acceptor
complexes,
more
recently
frustrated
Lewis
pairs.
Thus,
perfluoroalkylation
carbon–carbon
multiple
bonds,
isocyanides,
nitrones,
hydrazones,
β-keto
esters,
α-cyano
arylacetates,
sulfides,
(hetero)arenes
Special
emphasis
placed
examples
published
after
2015,
where
higher
fluorinated
series
fluoroalkylating
reagents
are
studied.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2019,
Volume and Issue:
7(11), P. 10154 - 10162
Published: May 9, 2019
A
mild
and
efficient
visible-light-induced
atom
transfer
radical
addition
cyclization
of
1,n-enynes
(n
=
6,
7)
with
perfluoroalkyl
halides,
leading
to
halo-perfluorinated
N-heterocycles,
has
been
developed.
This
protocol
offers
a
mild,
completely
atom-economic,
general
access
perfluorinated
2,4-dihydronquinolin-2(1H)-ones
pyrrolidines
from
corresponding
benzene
N-tethered
via
5∼6-exo-dig
cyclization,
allowing
for
the
expedient
incorporation
wide
variety
groups,
such
as
CF3,
i/n-C3F7,
n-C4F9,
n-C6F13,
n-C8F17,
n-C10F21,
CF2Br,
CF2CO2Et,
etc.
In
addition,
reactions
using
1,7-enynes
bearing
tert-butyl-linked
alkynyl
moiety
enable
divergent
involving
hydrogen
(HAT)
process,
thereby
novel
α,α-halo-perfluorinated
2,4-dihydronquinolin-2(1H)-ones.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(28), P. 15271 - 15275
Published: April 30, 2021
Abstract
Pentafluorosulfanyl
chloride
(SF
5
Cl)
is
the
most
prevalent
reagent
for
incorporation
of
SF
group
into
organic
compounds.
However,
preparation
Cl
often
relies
on
hazardous
reagents
and
specialized
apparatus.
Herein,
we
described
a
safe
practical
synthesis
bench‐stable
easy‐to‐handle
solution
in
n
‐hexane
under
gas‐reagent‐free
conditions.
The
synthetic
application
was
demonstrated
through
unprecedented
reaction
with
diazo
chemoselective
hydro‐
chloropentafluorosulfanylations
α‐diazo
carbonyl
compounds
were
developed
presence
K
3
PO
4
or
copper
catalyst,
respectively.
These
reactions
provide
direct
efficient
access
to
various
α‐pentafluorosulfanyl
high
value
potential
applications.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: July 16, 2021
Installation
of
fluorine
into
pharmaceutically
relevant
molecules
plays
a
vital
role
in
their
properties
biology
or
medicinal
chemistry.
Direct
difunctionalization
alkenes
and
1,3-dienes
to
achieve
fluorinated
compounds
through
transition-metal
catalysis
is
challenging,
due
the
facile
β-H
elimination
from
Csp3‒[M]
intermediate.
Here
we
report
cobalt-catalyzed
regioselective
difluoroalkylarylation
both
activated
unactivated
with
solid
arylzinc
pivalates
difluoroalkyl
bromides
cascade
Csp3‒Csp3/Csp3‒Csp2
bond
formation
under
mild
reaction
conditions.
Indeed,
wide
range
functional
groups
on
bromides,
olefins,
as
well
(hetero)arylzinc
are
tolerated
by
cobalt-catalyst,
thus
furnishing
three-component
coupling
products
good
yields
high
regio-
diastereoselectivity.
Kinetic
experiments
comparing
conventional
halides
highlight
unique
reactivity
these
organozinc
pivalates.
Mechanistic
studies
strongly
support
that
involves
direct
halogen
atom
abstraction
via
single
electron
transfer
situ
formed
cobalt(I)
species,
realizing
Co(I)/Co(II)/Co(III)
catalytic
cycle.
Nano Letters,
Journal Year:
2019,
Volume and Issue:
19(6), P. 3603 - 3611
Published: April 23, 2019
Due
to
the
combined
advantages
of
cellulose
and
nanoscale
(diameter
20–60
nm),
bacterial
possesses
a
series
attractive
features
including
its
natural
origin,
moderate
biosynthesis
process,
good
biocompatibility,
cost-effectiveness.
Moreover,
nanofibers
can
be
conveniently
processed
into
three-dimensional
(3D)
intertwined
structures
form
stable
paper
devices
after
simple
drying.
These
make
it
suitable
as
material
for
construction
organ-on-a-chip
using
matrix-assisted
sacrificial
3D
printing.
We
successfully
fabricated
various
microchannel
embedded
in
bulk
hydrogels
retained
their
integrity
drying
process.
Interestingly,
these
paper-based
containing
hollow
microchannels
could
rehydrated
populated
with
relevant
cells
vascularized
tissue
models.
As
proof-of-concept
demonstration,
we
seeded
human
umbilical
vein
endothelial
(HUVECs)
obtain
vasculature
inoculated
MCF-7
onto
surrounding
matrix
device
build
breast
tumor
model.
The
results
showed
that
were
perfusable,
both
HUVECs
exhibited
favorable
proliferation
behaviors.
This
study
may
provide
new
strategy
constructing
low-cost
vitro
models,
which
find
potential
applications
drug
screening
personalized
medicine.
Advanced Synthesis & Catalysis,
Journal Year:
2020,
Volume and Issue:
362(19), P. 3948 - 3970
Published: Aug. 1, 2020
Abstract
Transition‐metal‐catalyzed
1,2‐carbohalo‐functionalization
reactions
of
C−C
multiple
bonds
have
emerged
rapidly
over
the
past
decade
as
a
powerful
tool
for
generating
new
carbon‐carbon
and
carbon‐halogen
bond
via
transposition
an
existing
σ
bond.
Exploring
this
highly
efficient
mode
difunctionalization,
various
research
groups
established
novel
strategies
synthesis
organohalides
by
utilizing
wide
variety
transition
metal
catalysts
under
mild
reaction
conditions,
avoiding
stoichiometric
waste
by‐products,
with
improved
levels
chemo‐,
regio‐,
stereoselectivities.
Most
involve
either
reductive
elimination
mechanism
or
atom
transfer
radical
addition
(ATRA)
mechanism.
This
review
summarizes
recent
progress
in
area
transition‐metal‐catalyzed
intra‐
intermolecular
explicates
underlying
potentiality
challenges
within
field.
magnified
image
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(12), P. 2912 - 2968
Published: Feb. 5, 2021
Abstract
For
almost
40
years,
difluoromethylene
phosphonates
have
proven
to
be
versatile
molecular
tools
in
biochemical
studies
owing
their
close
resemblance
naturally
occurring
phosphates
and
phosphonates.
As
bioisosteric,
non‐hydrolyzable
analogs
of
these
essential
molecules,
can
target
the
critical
parts
cellular
machinery
therefore
exhibit
a
diverse
spectrum
biological
activity.
In
past
ten
there
appeared
many
new
methods
for
synthesis
Most
notably,
photoredox
catalysis
has
firmly
entered
field,
while
cross‐coupling
nucleophilic
strategies
met
considerable
elaboration
refinement,
entirely
accord
with
current
trends
synthetic
organic
chemistry.
Herein,
we
introduce
as
distinct,
high‐tech
subclass
resulting
from
research
efforts
on
cross‐section
organophosphorus,
organofluorine,
bioorganic
We
then
proceed
discussion
general
preparation
phosphonates,
comprehensively
reviewing
reactions
developed
15
years
providing
context
earlier
works
where
appropriate.
Finally,
present
selected
examples
molecules
high
activity,
targets,
steps
employed
preparation.
magnified
image
