Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(47), С. 9313 - 9318
Опубликована: Янв. 1, 2022
Fluoroalkenyl
moieties
are
often
used
as
carbonyl
mimics
in
medicine
preparation,
and
thus
the
development
of
facile
routes
for
synthesis
such
compounds
is
great
importance.
In
this
work,
we
report
a
photocatalytic
ring-opening
addition
cyclic
alcohols
to
α-(trifluoromethyl)styrenes,
which
underwent
proton-coupled
electron
transfer
β-scission
process,
delivering
variety
remote
gem-difluoroalkenyl
ketone
derivatives.
This
methodology
can
also
be
applied
reaction
gem-difluorostyrenes
1,1,2-trifluorostyrenes
access
monofluoro-
1,2-difluoroalkenyl
ketones.
ACS Catalysis,
Год журнала:
2023,
Номер
13(18), С. 12238 - 12268
Опубликована: Сен. 1, 2023
Organofluorine
compounds
have
attracted
extensive
attention
in
various
industrial
fields
due
to
their
unique
chemical
and
physical
properties.
Despite
increasing
demand
a
wide
range
of
scientific
fields,
the
synthesis
organofluorine
still
faces
several
problems,
such
as
difficulties
handling
fluorinating
reagents
control
chemoselectivity.
Compared
with
formation
C–F
bonds,
activation
functionalization
carbon–fluorine
bonds
is
very
important
but
challenging
topic
synthetic
chemistry.
Due
properties
nickel,
Ni-catalyzed
defluorinative
cross-couplings
been
greatly
developed
past
few
decades
powerful
strategies
for
construction
fluorinated
organic
compounds.
This
Review
summarizes
advances
cross-coupling
aryl
fluorides,
gem-difluorovinyl
trifluoromethyl
Green Chemistry,
Год журнала:
2023,
Номер
25(17), С. 6733 - 6738
Опубликована: Янв. 1, 2023
A
metal
free,
visible-light
driven
α-C(sp
3
)−H
gem-difluoroallylation
of
glycine
derivatives
with
CF
-alkenes
and
1,3-enynes
is
presented
under
redox-neutral
conditions
good
yields
excellent
functional
group
compatibility.
Trends in Chemistry,
Год журнала:
2023,
Номер
5(3), С. 174 - 200
Опубликована: Фев. 14, 2023
Organic
peroxides
are
becoming
popular
intermediates
for
novel
chemical
transformations.
The
weak
O-O
bond
is
readily
reduced
by
transition
metals,
including
iron
and
copper,
to
initiate
a
radical
cascade
process
that
breaks
C-C
bonds.
Great
potential
exists
the
rapid
generation
of
complexity,
originating
from
ability
couple
resulting
free
radicals
with
wide
range
partners.
First,
this
review
article
discusses
history
synthesis
organic
peroxides,
providing
context
necessary
understand
methodology.
Then,
it
highlights
91
examples
recent
applications
functionalization
bonds
accessed
through
metal-mediated
reduction
peroxides.
Finally,
we
provide
some
comments
about
safety
when
working
Organic Letters,
Год журнала:
2023,
Номер
25(31), С. 5756 - 5761
Опубликована: Июль 28, 2023
Herein
we
report
a
nickel-catalyzed
regioselective
cross-electrophile
ring
opening
reaction
of
sulfonyl-protected
aziridines
with
trifluoromethyl-substituted
alkenes
as
the
gem-difluoroallylating
agents,
providing
new
and
efficient
entry
to
prepare
gem-difluorobishomoallylic
sulfonamides.
Moreover,
scaffold
6-fluoro-1,2,3,4-tetrahydropyridine
can
be
constructed
starting
from
products
via
NaH-mediated
intramolecular
defluorinative
nucleophilic
vinylic
substitution.
Organic Letters,
Год журнала:
2023,
Номер
25(11), С. 1883 - 1888
Опубликована: Март 13, 2023
By
merging
C-C
and
C-F
bond
cleavage,
we
developed
a
regioselective
ring
opening/gem-difluoroallylation
of
cyclopropyl
ketones
with
α-trifluoromethylstyrenes,
which
proceeds
under
the
catalysis
iron
combination
manganese
TMSCl
as
reducing
agents,
providing
new
entry
to
synthesis
carbonyl-containing
gem-difluoroalkenes.
Remarkably,
ketyl
radical-induced
selective
cleavage
following
generation
more-stable
carbon-centered
radicals
enable
complete
regiocontrol
this
opening
reaction
for
various
substitution
patterns
cyclopropane
ring.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(8), С. 1165 - 1169
Опубликована: Март 24, 2023
Abstract
In
this
protocol,
we
apply
reductive
cobalt
catalysis
in
the
allylic
defluorinative
cross‐electrophile
coupling
reaction
between
1,1‐difluoroalkyl
halides
and
α‐trifluoromethyl
styrenes.
This
features
broad
substrate
scope
(39
examples),
good
tolerance
of
various
functionalities,
circumvention
pregenerating
organometallics,
offering
a
general
synthetic
route
to
prepare
diverse
organofluorines
incorporating
both
gem
‐difluoroalkene
‐difluoroalkane
moiety.
magnified
image
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(12), С. 1360 - 1366
Опубликована: Фев. 23, 2024
Comprehensive
Summary
The
conversion
of
CF
3
‐alkenes
to
gem
‐difluoroalkenes
using
reductive
cross‐coupling
strategy
has
received
much
attention
in
recent
years,
however,
the
use
green
and
readily
available
reducing
salt
mediate
these
reactions
remains
be
explored.
In
this
work,
a
concise
construction
gem‐
difluoroalkenes,
which
requires
neither
catalyst
nor
metal
agent,
was
established.
Rongalite,
safe
inexpensive
industrial
product,
employed
as
both
radical
initiator
reductant.
This
procedure
compatible
with
linear
cyclic
diaryliodonium
salts,
enabling
wide
variety
substrates
(>70
examples).
utility
approach
demonstrated
through
gram‐scale
synthesis
efficient
late‐stage
functionalizations
anti‐inflammatory
drugs.
Chemical Communications,
Год журнала:
2023,
Номер
59(88), С. 13175 - 13178
Опубликована: Янв. 1, 2023
An
NHC
organocatalytic
radical
acylation
of
cycloalkyl
silyl
peroxides
with
aldehydes
was
developed
for
the
efficient
and
rapid
synthesis
long-chain
1,6-/1,7-/1,8-diketones,
especially
unsymmetrical
ones.
Organic Letters,
Год журнала:
2025,
Номер
27(10), С. 2377 - 2382
Опубликована: Март 5, 2025
Direct
gem-difluoroallylation
at
the
α-carbonyl
position
is
a
challenging
process
by
conventional
methods.
Herein
we
report
photocatalytic
radical
α-C(sp3)─H
of
amides
with
trifluoromethyl
alkenes
to
access
target
compounds
good
yields
and
functional
group
tolerance.
The
mild
effective
conditions
allow
gem-difluoroalkene
motifs
as
carbonyl
bioisosteres
incorporated
concisely
some
complex
molecules,
including
gemfibrozil
estrone
derivatives,
presenting
great
potential
for
late-stage
functionalization
drugs,
natural
products,
bioactive
intermediates.
Mechanistic
investigations
suggest
pathway
combining
XAT
1,5-HAT.
