The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Herein,
we
described
the
addition
reactions
of
sulfur-containing
reagents
(sodium
sulfinates,
dithiosulfonates)
with
α-trifluoromethyl
alkenes
under
visible
light.
A
series
trifluoromethyl
sulfonates
were
synthesized
via
visible-light-induced
radical
reaction
sodium
sulfinates
and
to
obtain
protons
from
solvent.
dithiosulfonated
derivatives
bifunctionalization
dithiosulfonates.This
strategy
has
advantages
mild
conditions,
good
substrate
universality
high
yield
up
99%
yield.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(33)
Published: June 13, 2023
Abstract
The
difunctionalization
of
unsaturated
bonds
plays
a
vital
role
in
the
enrichment
molecular
complexity.
While
various
catalytic
methods
for
alkene
and
alkyne
have
been
developed
recent
years,
hetero‐functionalization
introduction
two
different
atoms
has
less
explored.
This
is
mainly
due
to
challenges
associated
with
achieving
high
chemo‐,
regio‐,
stereoselectivity,
especially
when
adding
similar
from
same
group
across
bonds.
In
this
study,
we
describe
nickel‐catalyzed,
three‐component
reductive
protocol
14
element
hetero‐difunctionalization
1,3‐enynes
using
electrochemistry.
new
method
mild,
selective,
general,
allowing
silyl‐,
germanyl‐,
stannyl‐alkylation
enynes.
Various
chlorosilanes
as
well
chlorogermans,
chlorostannanes
can
be
successfully
used
combination
aryl/alkyl‐substituted
primary,
secondary,
tertiary
alkyl
bromides
electroreductive
coupling.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(24), P. 5074 - 5081
Published: June 10, 2024
The
nickel/photoredox
dual
catalysis
system
is
an
efficient
conversion
platform
for
the
difunctionalization
of
unsaturated
hydrocarbons.
Herein,
we
disclose
first
nickel/photoredox-catalyzed
intramolecular
1,2-arylsulfonylation
allenes,
which
can
accurately
construct
a
C(sp2)–C(sp2)
bond
and
C(sp3)–S
bond.
reaction
exhibits
excellent
chemoselectivity
regioselectivity,
allowing
modular
conformations
diverse
series
3-sulfonylmethylbenzofuran
derivatives.
Control
experiments
showed
that
bipyridine
ligand
crucial
formation
stable
σ-alkyl
nickel
intermediate,
providing
possibility
sulfonyl
radical
insertion.
Meanwhile,
electrophilic
facilitates
further
oxidative
addition
intermediate
inhibits
with
allenes.
In
addition,
control
experiments,
cyclic
voltammetry
tests,
Stern–Volmer
density
functional
theory
calculations
afford
evidence
Ni(0)/Ni(I)/Ni(II)/Ni(III)
pathway
in
this
1,2-arylsulfonylation.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(11), P. 6578 - 6583
Published: Jan. 1, 2024
Using
sulfinic
acid
as
a
sulfonyl
source,
we
have
developed
light-promoted
photocatalyst-free
alkene
hydrosulfonylation
reaction
without
any
additives.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9283 - 9293
Published: June 4, 2024
The
direct
reductive
functionalization
of
alkynes
under
mild
conditions
presents
a
promising
yet
challenging
avenue
for
accessing
value-added
molecules.
Alkyne
radical
anions
represent
distinct
class
reactive
intermediates
characterized
by
both
charge
and
an
unpaired
electron,
thus
holding
great
potential
facilitating
diverse
bond
formations,
particularly
in
alkyne
functionalization.
However,
the
synthetic
utility
is
limited,
primarily
due
to
difficulty
their
generation
formation
highly
unstable
vinyl
intermediates.
In
this
study,
we
accomplished
from
aryl
feedstocks
via
single
electron
transfer
(SET)
reduction
with
photogenerated
CO2
anion
(CO2•–),
enabling
hydroalkylation,
arylalkenylation,
hydrocarboxylation
alkynes.
Our
photocatalytic
strategy
features
metal-free
catalysis,
reaction
conditions,
employment
traceless
reductant,
good
functional
group
compatibility,
step-
atom-economy,
high
regioselectivity.
This
study
not
only
paves
way
leveraging
underexplored
but
also
catalyzes
ongoing
exploration
bifunctional
CO2•–
species
chemistry.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(40), P. 27583 - 27593
Published: Sept. 26, 2024
The
exploration
of
strong
chemical
bonds
as
synthetic
handles
offers
new
disconnection
strategies
for
the
synthesis
functionalized
molecules
via
transition
metal
catalysis.
However,
slow
oxidative
addition
rate
these
covalent
to
a
center
hampers
their
utility.
Here,
we
report
C(sp
Molecules,
Journal Year:
2023,
Volume and Issue:
28(7), P. 3027 - 3027
Published: March 28, 2023
Radical
transformations
are
powerful
in
organic
synthesis
for
the
construction
of
molecular
scaffolds
and
introduction
functional
groups.
In
radical
difunctionalization
reactions,
radicals
first
functionalized
intermediates
can
be
relocated
through
resonance,
hydrogen
atom
or
group
transfer,
ring
opening.
The
resulting
undertake
following
paths
second
functionalization:
(1)
couple
with
other
groups,
(2)
oxidize
to
cations
then
react
nucleophiles,
(3)
reduce
anions
electrophiles,
(4)
metal-complexes.
rearrangements
provide
opportunity
1,3-,
1,4-,
1,5-,
1,6-,
1,7-difunctionalization
products.
Multiple
ways
initiate
reaction
coupling
intermediate
make
reactions
good
at
remote
positions.
These
offer
advantages
synthetic
efficiency,
operation
simplicity,
product
diversity.
