ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(22), P. 14106 - 14112
Published: Nov. 3, 2022
In
this
work,
we
report
manganese
porphyrin
complexes
for
the
electrocatalytic
vicinal
diazidation
of
alkenes
with
sodium
azide.
This
protocol
shows
improved
practicality
over
our
previous
work
using
MnBr2
catalysis
in
following
aspects:
(1)
it
requires
substantially
lower
catalyst
loading
(as
low
as
0.3
mol
%),
which
reduces
formation
metal
azide
and
simplifies
product
purification;
(2)
introduction
a
neutral
aqueous
buffer
prevents
generation
toxic
hydrazoic
acid,
contributing
to
safer
experimental
procedure;
(3)
catalytic
system
displays
reactivity
toward
unactivated
terminal
alkenes.
Mechanistic
studies
support
roles
second-sphere
hydrogen-bond
donors
stabilizing
key
reaction
intermediates.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
15(1), P. 124 - 133
Published: Nov. 24, 2023
Simple
iron
salts
are
able
to
photocatalyze
the
diazidation,
dichlorination,
and
fluorochlorination
of
alkenes
via
merger
ligand-to-metal
charge
transfer
(LMCT)
either
radical
ligand
(RLT)
or
fluorine
atom
(FAT).
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(44)
Published: Sept. 14, 2023
Herein,
an
electrochemically
driven
NiH-catalyzed
reductive
coupling
of
alkyl
halides
and
alkenes
for
the
construction
Csp3
-Csp3
bonds
is
firstly
reported.
Notably,
serve
dual
function
as
substrates
hydrogen
sources
to
generate
NiH
species
under
electrochemical
conditions.
The
tunable
nature
this
reaction
realized
by
introducing
intramolecular
coordinating
group
substrate,
where
product
can
be
easily
adjusted
give
desired
branched
products.
method
proceeds
mild
conditions,
exhibits
a
broad
substrate
scope,
affords
moderate
excellent
yields
with
over
70
examples,
including
late-stage
modification
natural
products
drug
derivatives.
Mechanistic
insights
offer
evidence
process.
sp3
-carbon-halogen
activated
through
single
electron
transfer
(SET)
nickel
catalyst
in
its
low
valence
state,
generated
cathodic
reduction,
generation
from
pivotal
transformation.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Oct. 13, 2023
Herein,
a
metal-free
electrochemical
dihydroxylation
of
unactivated
alkenes
is
described.
The
transformation
proceeds
smoothly
under
mild
conditions
with
broad
range
alkenes,
providing
valuable
and
versatile
dihydroxylated
products
in
moderate
to
good
yields
without
the
addition
costly
transition
metals
stoichiometric
amounts
chemical
oxidants.
Moreover,
this
method
can
be
applied
natural
pharmaceutical
derivatives,
further
demonstrating
its
synthetic
utility.
Mechanistic
studies
have
revealed
that
iodohydrin
epoxide
intermediate
are
formed
during
reaction
process.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(30), P. 8109 - 8118
Published: Jan. 1, 2023
The
chemical
up-cycling
of
polymers
into
value-added
materials
offers
a
unique
opportunity
to
place
plastic
waste
in
new
value
chain
towards
circular
economy.
Herein,
we
report
the
selective
polystyrenes
and
polyolefins
C(sp3)-H
azidated
under
electrocatalytic
conditions.
functionalized
were
obtained
with
high
retention
mass
average
molecular
functionalization
through
chemo-selective
mangana-electrocatalysis.
Our
strategy
proved
be
broadly
applicable
variety
homo-
copolymers.
Polyethylene,
polypropylene
as
well
post-consumer
polystyrene
by
this
approach,
thereby
avoiding
use
hypervalent-iodine
reagents
stoichiometric
quantities
means
electrocatalysis.
This
study,
hence,
represents
oxidant-free
polymer
electro-oxidation.
electrocatalysis
scalable,
which
highlights
its
feature
for
green
hydrogen
economy
evolution
reaction
(HER).
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(31), P. 5896 - 5901
Published: July 29, 2023
A
Cu-electrocatalytic
azidation
of
N-aryl
enamines
and
subsequent
denitrogenative
annulation
for
the
construction
quinoxaline
frameworks
is
reported.
Only
0.5
mol
%
copper(II)
chloride
was
employed
this
cascade
transformation
displaying
excellent
functional-group
compatibility
even
with
complex
bioactive
scaffolds.
The
efficient
electro-oxidative
protocol
enables
use
NaN3
as
cheapest
azide
source.
Detailed
mechanistic
experiments,
cyclic
voltammetry,
spectroscopic
studies
provided
strong
evidence
a
dual
role
Cu
catalyst
in
azidyl
iminyl
radical
generation
steps.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(27), P. 5162 - 5167
Published: June 29, 2023
A
visible-light-induced
cascade
arylazidation
of
activated
alkenes
with
trimethylsilyl
azide
(TMSN3)
has
been
developed.
Mechanistic
investigations
reveal
that
the
single
electron
transfer
(SET)
TMSN3
excited
photocatalyst
was
involved
in
initial
step,
followed
by
radical
addition/aryl
migration/desulfonylation
to
furnish
valuable
α-aryl-β-azido
amides
and
azidated
oxindoles
under
mild
conditions,
which
are
versatile
building
blocks
organic
synthesis.
With
simple
treatment,
obtained
arylazidated
products
were
further
converted
β-amino
amide
1,2,3-triazole
derivatives.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Dec. 13, 2023
An
electroreductive
strategy
for
radical
hydroxyl
fluorosulfonylation
of
alkenes
with
sulfuryl
chlorofluoride
and
molecular
oxygen
from
air
is
described.
This
mild
protocol
displays
excellent
functional
group
compatibility,
broad
scope,
good
scalability,
providing
convenient
access
to
diverse
β-hydroxy
sulfonyl
fluorides.
These
fluoride
products
can
be
further
converted
valuable
aliphatic
fluorides,
β-keto
β-alkenyl
Further,
some
these
showed
inhibitory
activity
against
Botrytis
cinerea
or
Bursaphelenchus
xylophilus,
which
could
useful
potent
agrochemical
discovery.
Preliminary
mechanistic
studies
indicate
that
this
transformation
achieved
through
rapid
O2
interception
by
the
alkyl
subsequent
reduction
peroxy
radical,
outcompete
other
side
reactions
such
as
chlorine
atom
transfer,
hydrogen
Russell
fragmentation.
