Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(10)
Published: Dec. 21, 2022
Abstract
Trifluoromethanesulfonic
anhydride
has
been
widely
used
in
synthetic
organic
chemistry,
not
only
for
the
conversion
of
various
oxygen‐containing
compounds
to
triflates,
but
also
electrophilic
activation
and
further
amides,
sulfoxides,
phosphorus
oxides.
In
recent
years,
utilization
Tf
2
O
as
an
activator
nitrogen‐containing
heterocycles,
nitriles
nitro
groups
become
a
promising
tool
development
new
valuable
methods
with
considerable
success.
addition,
efficient
radical
trifluoromethylation
trifluoromethylthiolation
reagent
due
contained
SO
CF
3
fragment,
significant
progress
made
this
area.
This
review
summarizes
applications
above
two
aspects,
aims
illustrate
role
potential
application
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(40)
Published: Aug. 16, 2023
Abstract
The
facile
construction
of
C(sp
3
)‐rich
carbo‐
and
heterocyclic
compounds
is
a
pivotal
synthetic
strategy
to
foster
contemporary
drug
discovery
programs.
downstream
dearomatization
readily
accessible
two‐dimensional
(2D)
planar
arenes
represents
direct
pathway
towards
accessing
three‐dimensional
(3D)
aliphatic
scaffolds.
Here,
we
demonstrate
that
polysulfide
anions
are
capable
catalyzing
process
substituted
naphthalenes,
indoles,
other
related
heteroaromatic
in
the
presence
potassium
formate
methanol
under
visible
light
irradiation.
developed
protocol
exhibits
broad
functional
group
tolerance,
operational
simplicity,
scalability,
cost‐effectiveness,
representing
practical
sustainable
tool
for
arene
dearomatization.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(10)
Published: Dec. 21, 2022
Abstract
Trifluoromethanesulfonic
anhydride
has
been
widely
used
in
synthetic
organic
chemistry,
not
only
for
the
conversion
of
various
oxygen‐containing
compounds
to
triflates,
but
also
electrophilic
activation
and
further
amides,
sulfoxides,
phosphorus
oxides.
In
recent
years,
utilization
Tf
2
O
as
an
activator
nitrogen‐containing
heterocycles,
nitriles
nitro
groups
become
a
promising
tool
development
new
valuable
methods
with
considerable
success.
addition,
efficient
radical
trifluoromethylation
trifluoromethylthiolation
reagent
due
contained
SO
CF
3
fragment,
significant
progress
made
this
area.
This
review
summarizes
applications
above
two
aspects,
aims
illustrate
role
potential
application
synthesis.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(7), P. 1192 - 1197
Published: Feb. 13, 2023
A
cost-effective,
highly
regioselective
and
metal-free
version
for
the
synthesis
of
indolizine
derivatives
by
means
Tf2O-mediated
cascade
reaction
pyridyl-enaminones
thiophenols/thioalcohols
under
mild
conditions
has
been
reported.
Diverse
electron-rich
could
be
obtained
in
up
to
94%
yield
via
selective
1,4-addition
vinyl
iminium
triflate
tandem
cyclization/aromatization,
which
allowed
simultaneous
construction
C–N
C–S/and
one
example
C–Se
bonds.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(18), P. 12935 - 12948
Published: Sept. 6, 2023
An
electrochemical
or
photoelectrochemical
regioselective
polyfluoroalkylation/cyclization
cascade
of
3-aza-1,5-dienes
with
sodium
fluoroalkanesulfinates
is
presented.
This
protocol
proceeds
a
broad
substrate
scope
and
good
functional
group
tolerance
under
mild,
oxidant-free,
transition-metal-free,
electrolyte-free
conditions
to
provide
3-polyfluoroalkylated
4-pyrrolin-2-ones
in
one
step
from
readily
available
N-vinylacrylamides,
it
scalable
the
Gram
scale.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(11), P. 7310 - 7321
Published: May 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 2815 - 2824
Published: Feb. 22, 2024
The
emergence
of
photocatalysis
has
greatly
advanced
radical
fluoroalkylation
reactions.
Central
to
this
advancement
is
the
introduction
and
refinement
reagents,
which
play
a
pivotal
role
in
driving
these
reactions
forward.
Intriguingly,
some
previously
not
recognized
for
their
properties,
have
emerged
as
key
players
area.
In
Perspective,
we
provide
an
overview
four
representative
reagents
pioneered
by
our
laboratory,
subsequently
garnered
extensive
application
broader
research
contexts,
including
difluorocarbene
precursors
bromodifluoromethylphosphonium
bromide,
electrophilic
sulfonylation
reagent
triflic
anhydride,
nucleophilic
trifluoromethylation
methyl
fluorosulfonyldifluoroacetate
(Chen's
reagent).
integration
phosphonium
into
enabled
unexpected
reactivities
now
notably
expanded
capabilities
difluoromethylation,
trifluoromethylation,
difluoroalkylation.
Our
discussion
highlights
how
atypical
enriched
toolkit
available
fluoroalkylations,
offering
insights
that
could
inspire
future
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1980 - 1984
Published: Feb. 29, 2024
Efforts
to
develop
alternatives
triflic
anhydride
(Tf2O)
as
a
trifluoromethylation
reagent
continue
due
its
limitations,
including
volatility,
corrosiveness,
and
moisture
sensitivity.
Described
herein
is
the
use
of
trifluoromethylsulfonylpyridinium
salt
(TFSP),
easily
obtained
by
one-step
reaction
Tf2O
with
4-dimethylaminopyridine,
for
trifluoromethylative
difunctionalization
alkenes
photoredox
catalysis.
DMSO
CH3CN
are
suitable
solvents
achieving
keto-
amino-trifluoromethylation
alkenes,
respectively,
good
functional
group
tolerance.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(3), P. 954 - 1014
Published: Dec. 14, 2023
The
review
summarises
various
photo-
and
electrochemical
strategies
for
trifluoromethylation
fluoroalkylation
of
different
C(sp
3
)–H,
2
C(sp)–H
bonds
in
several
classes
organic
molecules.
