Cell Reports Physical Science,
Journal Year:
2024,
Volume and Issue:
5(10), P. 102230 - 102230
Published: Oct. 1, 2024
Highlights•Ternary
EDA
exciplex
induced
alkyl
aryl
ether
synthesis•Aerobic
photocatalytic
system•Good
functional
group
compatibility
and
late-stage
functionalization•Scalable
synthesis
of
fine
chemicalsSummaryThe
direct
use
molecular
oxygen
as
a
clean,
abundant,
readily
available
reactant
is
one
the
green,
sustainable,
yet
challenging
methodologies
for
C–O
bond
construction
to
access
diverse
oxygenated
compounds.
Herein,
we
report
ternary
electron
donor-acceptor
complex
system
that
utilizes
O2
construct
multiple
bonds
successively
in
single-step
operation,
enabling
facile
assembly
ethers.
Mechanistic
investigation
shows
halide/2-tert-butyl-1,1,3,3-tetramethylguanidine/tetrahydrofuran
generated
situ
plays
an
essential
role,
affording
radical
anion
species
captured
by
electrophilic
form
Meisenheimer-type
intermediate,
subsequently
participates
Williamson
etherification
process
give
products
with
good
selectivity
compatibility.
This
protocol
not
only
enables
rapid
ethers
but
also
allows
chemicals,
such
proparacaine,
decylparaben,
sildenafil
subunits,
starting
from
halogenated
compounds.Graphical
abstract
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(4), P. 2358 - 2368
Published: Jan. 31, 2024
Conversion
of
potent
greenhouse
gases,
hydrofluorocarbons
(HFCs),
to
value-added
hydrofluoroolefins
(HFOs)
is
great
importance.
AlF3
catalysts
play
a
major
role
in
this
process.
Formation
and
maintenance
under
coordinated
Al
are
the
key
prepare
efficient
catalysts.
Herein,
carbon
interacted
nanoclusters
catalyst
(AlF3–SAPO-5)
was
effectively
achieved
with
SAPO-5
molecular
sieves
as
precursors
via
pyrolysis
followed
by
situ
fluorination.
This
process
results
strong
interaction
between
carbonaceous
material
active
aluminum
(Al)
species.
The
show
that
AlF3–SAPO-5
possesses
both
high
activity
thermal
stability.
For
1,1-difluoroethane
(HFC-152a)
dehydrofluorination,
conversion
can
reach
up
95%
at
reaction
temperature
350
°C.
rate
almost
4
times
higher
than
prepared
traditional
(AlF3-py).
It
implies
confinement
effect
contributes
formation
abundant
4-
5-coordinated
species
stabilized
F–Al–O–C
structure.
In
addition,
carbon-interacted
exhibit
superb
sintering
resistance.
Given
its
fantastic
stability,
potential
for
catalytic
dehydrofluorination
fluorinated
alkanes.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(8), P. 4518 - 4527
Published: Jan. 1, 2024
The
selection
of
electronically-different
thiolate-based
photosensitizers
is
employed
to
achieve
a
precise
and
specific
C–F
bond
defluorination
broad
range
trifluoromethylarenes,
enabling
the
synthesis
88
α,α-difluoromethyl
compounds.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
16(8)
Published: Dec. 28, 2023
Abstract
The
selective
C−F
bonds
functionalization
in
available
trifluoromethyl
compounds
is
an
economic
route
for
obtaining
high‐value
organic
fluorine
compounds.
However,
due
to
the
high
dissociation
energy
group,
strength
of
bond
decreases
continuously
during
defluorination,
posing
a
challenge
modifying
such
molecules
without
over‐conversion.
Over
past
few
years,
there
has
been
significant
progress
developing
efficient
methods
constructing
difluoromethylene
unit,
using
approaches
as
radical
chemistry,
photochemistry,
electrochemistry,
and
organometallic
chemistry.
These
involve
difluorocarbon
radicals,
cations,
anions,
carbenes
intermediates.
In
this
review,
we
summarized
recent
five
years
research
achievements
field
single
cleavage
aromatic
carbonyl
gain
diverse
difluoromethylene‐containing
via
different
intermediate
strategies.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12591 - 12609
Published: Aug. 14, 2024
The
incorporation
of
gem-difluoromethylene
units
into
organic
molecules
remains
a
formidable
challenge.
Conventional
methodologies
for
constructing
aryldifluoromethyl
derivatives
relied
on
the
use
high-functional
fluorinating
regents
under
harsh
conditions.
Herein,
we
report
general
and
efficient
photoredox
catalytic
systems
defluoroalkylation
readily
available
trifluoromethylarenes
through
selective
C–F
cleavage
to
deliver
gem-difluoromethyl
radicals
which
proceed
reductive
addition
both
electron-donating
withdrawing
alkenes
transition-metal
free
Mechanistic
studies
reveal
that
thiol
serves
as
photocatalyst
HAT
reagent
visible
light
irradiation.
This
synergistic
photocatalysis
catalysis
protocol
exhibits
ample
salient
features
such
high
chemo-
regioselectivity,
broad
substrate
scope,
amenable
gram-scale
synthesis
late-stage
modification
bioactive
molecules.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(18), P. 4542 - 4549
Published: Jan. 1, 2023
A
visible-light-induced
alkylamine-facilitated
reductive
defluoroallylation
of
difluoromethyl
ketones
with
allylic
chlorides
is
reported,
enabling
efficient
access
to
α-fluoro
alkenylketones
high
efficiency.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(33)
Published: April 11, 2024
Photoinduced
single-electron
reduction
is
an
efficient
method
for
the
mono-selective
activation
of
C-F
bond
on
a
trifluoromethyl
group
to
construct
difluoroalkyl
group.
We
have
developed
electron-donor-acceptor
(EDA)
complex
mediated
transfer
(EDA-SET)
α,α,α-trifluoromethyl
arenes
in
presence
lithium
salt
give
α,α-difluoroalkylarenes.
The
was
realized
by
iodide
and
triethylamine,
two
common
feedstock
reagents.
Mechanistic
studies
revealed
generation
α,α-difluoromethyl
radical
defluorination,
followed
addition
alkenes.
Lithium
interacted
with
fluorine
atom
promote
photoinduced
EDA
complex.
Computational
indicated
that
lithium-assisted
defluorination
occurred
concertedly.
call
this
phenomenon
fluoride-coupled
electron
(FCET).
FCET
novel
approach
synthesis
organofluorine
compounds.
