Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
136(7)
Published: Dec. 22, 2023
Abstract
Radical
trifluoromethoxylation
is
an
attractive
approach
to
prepare
compounds
featuring
the
important
OCF
3
group,
however
most
existing
methods
have
focused
on
aromatic
substrates.
Here,
we
report
novel
methodologies
with
alkenyl
substrates
employing
bis(trifluoromethyl)peroxide
(BTMP)
as
a
practical
and
comparatively
atom
economical
trifluoromethoxylating
reagent.
With
silyl
enol
ether
substrates,
switching
reaction
solvent
allows
for
synthesis
of
either
α‐(trifluoromethoxy)ketone
products
or
unprecedented
alkenyl‐OCF
species.
Furthermore,
allyl
silanes
been
employed
first
time,
affording
allyl(trifluoromethyl)ether
in
good
yields.
In
each
case,
operate
at
room
temperature
without
large
excesses
alkene
substrate
while,
contrast
previous
radical
reactions,
no
catalyst,
light
other
activators
are
required.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(17), P. 2179 - 2196
Published: April 25, 2023
Comprehensive
Summary
The
trifluoromethoxy
functional
group
has
received
increasing
attention
in
recent
years
due
to
its
distinctive
properties
such
as
good
metabolic
stability,
appropriate
lipophilicity
and
special
electrical
properties.
Thus,
the
development
of
new
reagents
strategies
direct
trifluoromethoxylation
are
attracting
enthusiasm
many
fluorine
chemical
workers.
At
present,
nucleophilic
radical
trifluoromethoxylating
have
made
major
breakthroughs,
greatly
promoting
chemistry.
This
review
is
mainly
divided
into
two
parts:
types,
focusing
on
history,
characteristics
applications
various
reagents.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2325 - 2332
Published: Jan. 17, 2024
The
only
known
method
for
the
dearomative
trifluoromethoxylation
of
indoles
is
preliminary,
with
one
substrate
successfully
undergoing
reaction.
In
this
study,
we
not
developed
a
broadly
applicable
indole
but
also
achieved
divergent
by
fine-tuning
reaction
conditions.
Under
optimized
conditions,
silver
salt
and
an
easily
handled
OCF3
reagent,
various
smoothly
underwent
dearomatization
to
afford
diverse
array
ditrifluoromethoxylated
indolines
in
50–84%
isolated
yields
up
37:1
diastereoselectivity,
fluorinated
trifluoromethoxylated
were
obtained
exclusive
trans
selectivity.
addition,
conditions
compatible
other
heteroaromatic
rings
as
well
styrene
moieties.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(18)
Published: March 2, 2023
Due
to
the
strong
electron-withdrawing
nature
and
high
lipophilicity
of
trifluoromethoxy
group
(OCF3
),
methods
for
introducing
OCF3
into
organic
molecules
are
in
demand.
However,
research
area
direct
enantioselective
trifluoromethoxylation
is
still
embryonic
stage,
with
limited
enantioselectivity
and/or
reaction
types.
Here,
we
describe
first
copper-catalyzed
propargyl
sulfonates
using
trifluoromethyl
arylsulfonate
(TFMS)
as
source
up
96
%
ee.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(9), P. 1405 - 1412
Published: April 7, 2023
Abstract
Fluoroalkyl
ethers
have
attracted
considerable
research
interest
in
the
fields
of
pharmaceutical,
agrochemical,
nuclear
imaging
and
material
sciences,
forging
development
new
synthetic
methods
to
access
this
class
compounds.
Radical
fluoroalkoxylation
has
recently
emerged
as
a
promising
approach
for
synthesizing
fluoroalkyl
ethers.
Herein,
solid,
easy‐to‐access
redox‐active
N−O
reagent,
1‐(fluoromethoxy)‐3‐methyl‐benzotriazolium
triflate
(FMBT),
serving
radical
source
(mono)fluoromethoxy
group
under
photocatalytic
conditions,
was
introduced.
The
potential
FMBT
demonstrated
functionalization
olefins
amino
keto‐monofluoromethyl
ethers,
benefiting
related
study
context
chemical
biology
drug
discovery.
magnified
image
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(24), P. 4926 - 4954
Published: Jan. 1, 2023
Fluorinated
organic
compounds
are
an
important
class
of
molecules
and
play
a
key
role
in
both
academic
industrial
communities
due
to
the
unique
nature
fluorine.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(58)
Published: July 26, 2022
Abstract
Direct
fluoroalkoxylation
reactions
of
(hetero)arenes,
carbon‐carbon
multiple
bonds,
and
substitution
at
Csp
3
carbon
centers
by
CF
O,
CHF
2
(CF
)
CFO
groups
are
discussed.
Emphasis
on
thermal
radical,
electron
transfer,
photocatalytic,
electrochemical
redox‐neutral
radical
methods
placed
to
accomplish
reactions.
All
these
employ
either
fluoroalkoxylating
reagents
or
some
nucleophilic
trifluoromethoxylating
sources
O.
A
summary
all
is
provided
in
Table
2.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(7), P. 4434 - 4441
Published: March 15, 2023
Due
to
the
unique
properties
of
OCF3
group,
trifluoromethyl
ether
compounds
play
an
important
role
in
pharmaceuticals
and
agrochemicals.
Recently,
considerable
attention
has
been
focused
on
development
practical
convenient
reagents
for
direct
incorporation
group
into
organic
compounds.
Herein,
we
reported
a
new
trifluoromethoxylating
reagent
N-trifluoromethoxyphthalimide
(Phth-OCF3).
The
was
stable
solid
released
anion
under
mild
reaction
conditions.
We
demonstrated
application
Phth-OCF3
nucleophilic
trifluoromethoxylation
various
alkyl
electrophiles.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(3), P. 881 - 885
Published: Jan. 13, 2022
We
disclose
a
silver-catalyzed
trifluoromethoxylation
of
N-tosyl
aziridines
with
trifluoromethyl
arylsulfonate.
The
protocol
is
characterized
by
its
mild
conditions,
simple
operations,
and
good
chemo-
regioselectivity.
In
addition,
the
trisubstituted
could
construct
C-OCF3
quaternary
centers
exclusively,
which
quite
rare.
This
method
unlocks
new
catalytic
blueprint
for
accessing
β-trifluoromethoxylated
amines,
be
important
building
blocks
in
synthetic
chemistry.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(25), P. 9574 - 9581
Published: Jan. 1, 2024
The
synthesis
of
long-chain
perfluoroalkyl
ethers
remains
a
challenge.
stabilization
longer-chain
perfluoroalkoxides
with
triglyme-encapsulated
potassium
ions
enabled
the
bis(α,α-difluoro)ethers
gem
-difluoroalkenes.
Symmetry,
Journal Year:
2021,
Volume and Issue:
13(12), P. 2380 - 2380
Published: Dec. 10, 2021
This
review
provides
a
short
summary
of
the
traditional
methods
for
synthesis
CF3-O-containing
compounds,
followed
by
critical
overview
known
trifluoromethoxylating
reagents,
focusing
on
their
preparation,
synthetic
generality
and
limitations.
