Angewandte Chemie,
Год журнала:
2021,
Номер
133(21), С. 11885 - 11889
Опубликована: Март 4, 2021
Abstract
Direct
allylic
C−H
thiolation
is
straightforward
for
C(sp
3
)−S
bond
formation.
However,
strong
interactions
between
thiol
and
transition
metal
catalysts
lead
to
deactivation
of
the
catalytic
cycle
or
oxidation
sulfur
atom
under
oxidative
condition.
Thus,
direct
)−H
has
proved
difficult.
Represented
herein
an
exceptional
direct,
efficient,
atom‐
step‐economic
S−H
visible
light
irradiation.
Radical
trapping
experiments
electron
paramagnetic
resonance
(EPR)
spectroscopy
identified
radical
thiyl
generated
on
surface
photocatalyst
quantum
dots
(QDs).
The
C−S
formation
does
not
require
external
oxidants
initiators,
hydrogen
(H
2
)
produced
as
byproduct.
When
vinylic
was
used
instead
bond,
radical‐radical
cross‐coupling
achieved
with
liberation
H
.
Such
a
unique
transformation
opens
up
door
toward
coupling
valuable
organosulfur
chemistry.
iScience,
Год журнала:
2025,
Номер
28(3), С. 111976 - 111976
Опубликована: Фев. 10, 2025
1,n-Dual
Π
systems
including
1,4-diene
derivatives
have
been
widely
used
as
the
elegant
radical
receptors
to
promote
cascade
additions
give
highly
functionalized
polycyclic
scaffolds.
However,
tedious
and
complicated
preparation
of
former
deters
broad
utilization
compromises
practical
value.
Herein,
a
straightforward
was
developed
from
easily
accessible
alkynes
γ,δ-unsaturated
carboxylic
acids
via
electrochemical
oxidation
cyclization
Hofmann
elimination.
This
transformation
features
with
good
excellent
yields,
functional
group
compatibility,
selectivity
without
any
Zaitsev
elimination
product
detected.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 20, 2025
Direct
C-H
bond
functionalization
has
emerged
as
one
of
the
most
powerful
and
practical
strategies
for
modification
drug
molecules.
We
have
recently
disclosed
a
Cu/NFAS
(NFAS
=
N-fluoroalkyl
sufonamide)
catalytic
system
that
exhibits
high
site-,
regio-,
enantioselectivity
direct
cyanation
allylic
bonds.
Here,
we
present
mechanistic
investigation
this
catalyst
system,
including
elucidation
side
reactions
involved
in
transformation.
This
work
focuses
on
an
in-depth
analysis
cycle
based
kinetic
studies
by
NMR
spectroscopy
characterization
speciation
EPR
UV-vis
spectroscopy.
These
indicate
fraction
NFAS
is
sacrificed
to
Cu(II)-bounded
N-centered
radical
(Cu(II)-NCR)
species
generation
silylated
sulfonamides
(CN)2.
The
data
also
show
great
dependence
reaction
yield
selectivity
(hydrogen
atom
abstraction
or
HAA
over
reactions)
structure
Cu(II)-NCR
species.
Kinetic
DFT
calculations
further
reveal
oxidation
CuCN
NFAS,
process,
Cu(II)-NCRs
with
TMSCN
comparable
energy
barriers,
which
collectively
determine
rate
overall
reaction.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(22)
Опубликована: Май 11, 2022
Abstract
Metal/metal
dual
catalysis
provides
new
viewpoints
and
opportunities
for
C−H
functionalization,
especially
in
reactivity
selectivity
control
aspects.
It
helps
to
realize
sequential
or
cooperative
catalytic
transformations
one‐pot,
shortening
the
synthetic
steps
target
molecules
construction.
This
micro‐review
summarizes
most
recent
advances
this
research
field,
discusses
related
mechanism,
collecting
examples
according
role
of
metal
species.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(13), С. 3275 - 3279
Опубликована: Янв. 1, 2023
Allylic
C(sp
3
)–H
alkylation
of
α-alkylstyryl
sulfonium
salts
based
on
[2,3]-sigmatropic
rearrangement
strategies
has
been
developed.
This
protocol
could
allow
facile
access
to
allylated
carbon
quaternary
centers
in
moderate
good
yields.
Angewandte Chemie,
Год журнала:
2021,
Номер
133(21), С. 11885 - 11889
Опубликована: Март 4, 2021
Abstract
Direct
allylic
C−H
thiolation
is
straightforward
for
C(sp
3
)−S
bond
formation.
However,
strong
interactions
between
thiol
and
transition
metal
catalysts
lead
to
deactivation
of
the
catalytic
cycle
or
oxidation
sulfur
atom
under
oxidative
condition.
Thus,
direct
)−H
has
proved
difficult.
Represented
herein
an
exceptional
direct,
efficient,
atom‐
step‐economic
S−H
visible
light
irradiation.
Radical
trapping
experiments
electron
paramagnetic
resonance
(EPR)
spectroscopy
identified
radical
thiyl
generated
on
surface
photocatalyst
quantum
dots
(QDs).
The
C−S
formation
does
not
require
external
oxidants
initiators,
hydrogen
(H
2
)
produced
as
byproduct.
When
vinylic
was
used
instead
bond,
radical‐radical
cross‐coupling
achieved
with
liberation
H
.
Such
a
unique
transformation
opens
up
door
toward
coupling
valuable
organosulfur
chemistry.
