Bi-Catalyzed Trifluoromethylation of C(sp2)–H Bonds under Light
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(47), P. 25538 - 25544
Published: Nov. 14, 2023
We
disclose
a
Bi-catalyzed
C–H
trifluoromethylation
of
(hetero)arenes
using
CF3SO2Cl
under
light
irradiation.
The
catalytic
method
permits
the
direct
functionalization
various
heterocycles
bearing
distinct
functional
groups.
structural
and
computational
studies
suggest
that
process
occurs
through
an
open-shell
redox
manifold
at
bismuth,
comprising
three
unusual
elementary
steps
for
main
group
element.
cycle
starts
with
rapid
oxidative
addition
to
low-valent
Bi(I)
catalyst,
followed
by
light-induced
homolysis
Bi(III)–O
bond
generate
trifluoromethyl
radical
upon
extrusion
SO2,
is
closed
hydrogen-atom
transfer
Bi(II)
intermediate.
Language: Английский
Iron(II) triflate as a photocatalyst for trifluoromethylation of functionalized arenes under blue LED light: Access to bioactive compounds
Journal of Catalysis,
Journal Year:
2024,
Volume and Issue:
434, P. 115506 - 115506
Published: April 20, 2024
Language: Английский
Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis
Published: Aug. 16, 2023
Trifluoroacetates
are
the
most
abundant
and
accessible
sources
of
trifluoromethyl
groups,
which
key
components
in
pharmaceuticals
agrochemicals.
The
generation
reactive
radicals
from
trifluoroacetates
requires
their
decarboxylation,
is
hampered
by
high
oxidation
potential.
This
constitutes
a
major
challenge
for
redox-based
methods,
because
need
to
pair
redox
potentials
with
trifluoroacetate.
Here
we
report
strategy
based
on
iron
photocatalysis
promote
direct
photodecarboxylation
that
displays
reactivity
features
escape
limitations.
Our
synthetic
design
has
enabled
use
trifluoromethylation
more
easily
oxidizable
organic
substrates,
offering
new
opportunities
late-stage
derivatization
campaigns
using
chemical
feedstocks,
Earth-abundant
catalysts,
visible-light.
Language: Английский