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.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(64)
Published: Aug. 24, 2023
A
scalable
straightforward
synthesis
of
monofluoro-
and
difluoromethyl
triflate
CF3
SO2
OCH2
F
(MH2F
)
OCHF2
(MHF2
through
electrochemical
fluorination
(ECF,
Simons
process)
methyl
MH3
in
anhydrous
hydrogen
fluoride
at
nickel
anodes
is
presented.
The
ECF
method
also
feasible
for
the
preparation
deuterated
analogues
OCD2
(MD2F
OCDF2
).
Surprisingly,
no
H/D
exchange
occurs
during
OCD3
(MD3
);
this
provides
further
evidence
a
NiF3
/NiF4
-mediated
mechanism.
selected
partially
fluorinated
ethyl
triflates
described,
(EH2F3
leads
to
until
now
unknown
chiral
OCHFCF3
(EHFF3
analogous
fluoromethyl
fluoroethyl
nonaflates
are
accessible
by
ECF.
This
study
contains
detailed
spectroscopic,
structural,
thermal
data
on
(fluoro)methyl
fluoro(ethyl)
triflates.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(18)
Published: March 2, 2023
Abstract
Due
to
the
strong
electron‐withdrawing
nature
and
high
lipophilicity
of
trifluoromethoxy
group
(OCF
3
),
methods
for
introducing
OCF
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.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(32), P. 6588 - 6594
Published: Jan. 1, 2023
A
practical
synthesis
of
new
β-difluoromethoxy
vinyl
sulfones
has
been
explored
by
O-difluoromethylation
β-ketosulfones
using
the
inexpensive
and
easily
workable
sodium
chlorodifluoroacetate
as
a
difluorocarbene
precursor.
The
strategy
is
convenient
regioselective,
features
an
adequate
substrate
scope
functional
group
tolerance.
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.
