Abstract
An
expedient
strategy
for
the
construction
of
trifluoromethylselenolated
spiro[5.5]trienones/spiro[4.5]trienones
through
a
cascade
electrophilic
trifluoromethylselenolation
cyclization
and
dearomatization
has
been
developed.
This
sequential
process
was
induced
by
N
‐trifluoromethylselenophthalimide
(Phth‐SeCF
3
),
which
an
efficient
reagent.
approach
feature
mild
conditions,
broad
substrate
scope,
high
functional
group
tolerance.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
gem-Difluorohomoallyl
amines,
an
important
class
of
gem-difluoroalkenes,
are
prevalent
moieties
in
many
bioactive
compounds.
However,
limited
methods
suitable
for
the
synthesis
this
type
compound
containing
secondary
amines.
Here,
we
display
a
photocatalytic
multicomponent
protocol
gem-difluoroalkenes
which
makes
use
readily
available
materials:
arylamines,
alkyl
aldehydes,
and
α-trifluoromethyl
alkenes.
Moreover,
ketones
amines
also
substrates.
Preliminary
mechanistic
experiments
indicate
that
key
α-amino
radical
was
involved,
generated
from
reduction
situ-formed
imines
(or
iminium
ions)
by
reduced
photocatalyst.
Subsequent
addition
to
alkenes
β-F
elimination
deliver
desired
products.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 2939 - 2944
Published: April 11, 2024
A
selective
three-component
1,2-sulfonyl
etherification
of
aryl
1,3-dienes
enabled
by
copper
catalysis
to
afford
biologically
interesting
alkenyl
1,2-sulfone
ether
derivatives
through
C–S
and
C–O
bond
formation
is
described.
The
protocol
proceeds
with
the
sulfonyl
chloride
alcohols
under
simple,
mild,
base-free
conditions,
providing
a
straightforward
route
sulfonylated
allyl
compounds
broad
functional
group
tolerance
excellent
chemo-
regioselectivity.
Mechanistic
studies
indicate
that
alkene
difunctionalization
includes
key
copper-mediated
single-electron
transfer
process.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(18), P. 2203 - 2210
Published: May 14, 2024
Comprehensive
Summary
Compared
to
well‐established
1,5‐HAT
of
N
‐centered
radicals,
the
synthetic
applications
1,2‐HAT
process
were
scarce
due
high
barrier
and
constrained
three‐membered
transition
state.
Here,
we
have
developed
a
novel
C(sp
3
)‐H
gem
‐difluoroallylation
via
base
assisted
formal
amidyl
radicals
with
reductive
quenching
cycle
photocatalyst.
This
transformation
enables
efficient
formation
α‐aminoalkyl
showcases
good
functional
group
tolerance.
Our
preliminary
mechanistic
experiments,
along
Density
Functional
Theory
(DFT)
calculations
demonstrate
feasibility
especially
when
by
base.
Furthermore,
our
method
also
succeeds
in
Giese
addition
electron‐deficient
alkenes
as
well
styrene.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(10), P. 2075 - 2080
Published: Jan. 1, 2024
Direct
C(sp
3
)-H
selenation,
which
is
most
atom
economical,
remains
a
formidable
challenge,
and
only
few
examples
have
been
reported
to
date.
In
this
article,
we
introduce
the
transition
metal-free
selenation
with
β-ketosulfones
diselenides
as
material
source.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 25, 2025
p-CF3BnSeCF2Br
was
developed
as
a
bromodifluoromethylselenonating
reagent,
which
utilized
by
combining
with
mCPBA
and
Tf2O
for
the
synthesis
of
4-(bromodifluoromethylseleno)
isocoumarins
via
selenolation/lactonization
2-alkynylbenzoates.
The
transformation
postulated
to
proceed
multicomponent
reagents
system-enabled
sequence
involving
oxidation
into
its
selenium
sulfoxide,
activation
generated
sulfoxide
electrophilic
p-CF3BnSeOCF2Br
salt,
2-alkynylbenzoates
reactive
species
isocoumarins.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 9372 - 9380
Published: June 21, 2023
Visible-light-induced
decarboxylative
trifluoromethylselenolation
of
(hetero)aromatic
carboxylic
acids
with
[Me4N][SeCF3],
oxidant,
and
catalysts
afforded
a
variety
(hetero)aryl
trifluoromethyl
selenoethers
in
good
yields.
The
reaction
might
involve
radical
process,
which
generated
radicals
from
the
stable
via
oxidative
decarboxylation
NFSI
as
[di-tBu-Mes-Acr-Ph][BF4]
photocatalyst,
1,1'-biphenyl
cocatalyst.
Both
had
decisive
influence
on
reaction.
was
further
promoted
by
copper
salts
probably
Cu-mediated
cross-coupling
sensitive
SeCF3
species
situ
formed
radicals.
Advantages
method
include
visible
light
irradiation,
mild
conditions
at
ambient
temperature,
functional
group
tolerance,
no
pre-functionalization/activation
starting
acids,
applicability
to
drug
molecules.
This
protocol
is
promising
synthetically
useful,
overcame
limitations
known
methods
represented
first
acids.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(41)
Published: May 8, 2023
Herein,
the
tandem
synthesis
of
various
CF3
Se-containing
heterocyclic
compounds
has
been
developed,
using
Tf2
O
as
catalyst
and
trifluoromethyl
selenoxides
electrophilic
trifluoromethylselenolation
reagents.
This
process
is
characterized
by
its
mild
conditions,
ease
operation,
good
functional
group
compatibility.
A
variety
alkynes
could
be
transferred
into
indoles,
benzofurans,
benzothiophenes,
isoquinolines
chromenes
in
yields.
key
step
involving
formation
Se
species
was
proposed.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(38)
Published: Aug. 3, 2023
Abstract
Due
to
their
high
lipophilicity
and
strong
electron‐withdrawing
property,
more
attention
has
been
paid
introducing
trifluoromethylseleno
fluoroalkylseleno
moieties
into
organic
molecules.
In
this
short
review,
we
categorize
the
synthesis
of
compounds
that
combine
selenium
fluorinated
two
main
types:
trifluoromethylselenolation
(CF
3
Se)
fluoroalkylselenolation
(R
f
Se,
except
CF
Se).
This
review
aims
provide
a
summary
recent
advances
in
direct
C−H
from
reagents
application.
Based
on
method
how
R
Se
group
was
introduced,
content
is
divided
three
parts:
transition‐metal‐free
reactions,
transition‐metal‐mediated/catalyzed
reactions
photo‐catalyzed
reactions.
The
general
substrate
scope,
mechanism
limitations
would
also
be
discussed
so
hope
will
serve
as
an
inspiration
for
further
research
appealing
field.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(43), P. 7884 - 7889
Published: Oct. 25, 2023
A
visible-light-induced
metal-free
trifluoromethylselenolation
of
aryl
iodides
and
bromides
with
[Me4N][SeCF3]
is
described.
The
reaction
was
conducted
at
ambient
temperature
by
successfully
harnessing
the
light-sensitive
SeCF3
reagent.
Mechanistically,
EDA
complexes
between
halide
-SeCF3
anion
or
base
might
be
formed
excited
light,
which
subsequently
undergo
intracomplex
SET
processes
to
generate
•SeCF3
radicals
as
key
intermediates,
allowing
a
convenient
green
access
various
trifluoromethyl
selenoethers.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(19), P. 4905 - 4911
Published: Jan. 1, 2023
Herein,
we
have
reported
a
metal-free
Lewis-acid-catalyzed
divergent
trifluoromethylselenolation
of
alkynes
to
construct
α-trifluoromethylselenolated
ketones
and
trifluoromethylselenolated
alkynes.
