Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(7), P. 2828 - 2832
Published: March 24, 2020
Here
we
report
a
method
for
the
site-selective
intermolecular
C(sp3)-H
amination
of
carboxamides
by
merging
transition-metal
catalysis
and
hydrogen
atom
transfer
strategy.
The
reaction
proceeds
through
sequence
favorable
single-electron
transfer,
1,5-hydrogen
C-N
cross-coupling
steps,
thus
allowing
access
to
series
desired
products.
This
could
accommodate
wide
diversity
nitrogen
nucleophiles
as
well
demonstrate
excellent
chemoselectivity
functional
group
compatibility.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(17)
Published: Feb. 21, 2023
Represented
herein
is
the
first
example
of
N-radical
generation
direct
from
N-H
bond
activation
under
mild
and
redox-neutral
conditions.
The
in
situ
generated
intercepts
a
reduced
heteroarylnitrile/aryl
halide
for
C-N
formation
visible-light
irradiation
quantum
dots
(QDs).
A
series
aryl
alkylamines
with
heteroarylnitriles/aryl
halides
exhibit
high
efficiency,
site-selectivity
good
functional-group
tolerance.
Moreover,
consecutive
C-C
using
benzylamines
as
substrates
also
achieved,
producing
N-aryl-1,2-diamines
H2
evolution.
conditions,
broad
substrate
scope,
efficiency
are
advantageous
organic
synthesis.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(7), P. 976 - 982
Published: March 2, 2023
Abstract
Readily
available,
sterically,
and
electronically
tunable
sulfonamides
have
been
developed
as
effective
photoinduced
hydrogen
atom
transfer
(HAT)
catalysts
for
selective
Si−H
functionalizations
of
a
broad
range
silanes.
N
‐centered
radicals,
catalytically
generated
from
by
photoredox
catalyzed
single‐electron
oxidation,
are
the
key
intermediates
that
enable
an
HAT
process
silyl
radical
generation
to
achieve
hydrosilylation
activated
alkenes.
Additionally,
this
catalytic
system
can
also
be
applied
activation
Ge−H
bond
hydrogermylation
alkenes
through
sulfonamide
derived
nitrogen
centered
radical.
The
ability
generate
germyl
using
photochemical
offers
new
avenue
towards
sustainable
synthesis
organosilicon
organogermanium
compounds.
magnified
image
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(13), P. 2898 - 2918
Published: May 18, 2024
Abstract
Converting
any
desired
C−H
bond
to
the
intended
C−Z
in
a
given
organic
molecule
could
be
final
peak
of
functionalization
methodology.
Among
three
types
bonds,
ubiquitous
C(
sp
3
)−H
has
gained
particular
attention,
especially
last
two
decades.
There
are
different
ways
transform
bonds
into
bonds.
The
use
chlorine
radicals
is
one
these
methods
with
promising
future.
literature
review
shows
that
sources
have
been
used
for
chlorine,
including
chloride
ions
(HCl
or
salts),
coordinated
chlorides
(transition
metal
complexes),
and
(organochlorine
compounds).
However,
HCl
FeCl
most
attention
among
sources.
major
convert
from
radicals:
1)
oxidation
hydrogen
salts,
2)
photolysis
chloride,
3)
transition
insertion
C−Cl
This
summarizes
published
research
papers
on
functionalization.
Therefore,
chlorination
reactions
which
do
not
play
direct
role
cleavage
within
scope
this
review.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 14, 2024
Abstract
The
generation
of
alkyl
radical
from
C(sp
3
)−H
substrates
via
hydrogen
atom
abstraction
represents
a
desirable
yet
underexplored
strategy
in
alkylation
reaction
since
involving
common
concerns
remain
adequately
unaddressed,
such
as
the
harsh
conditions,
limited
substrate
scope,
and
employment
noble
metal-
or
photo-catalysts
stoichiometric
oxidants.
Here,
we
utilize
synergistic
photoredox
transfer
(HAT)
catalysis
to
accomplish
general
practical
functionalization
unactived
centers
with
broad
high
functional
group
compatibility,
operational
simplicity.
A
combination
validation
experiments
density
theory
reveals
that
N-centered
radicals,
generated
free
N
−
H
bond
stepwise
electron/proton
event,
are
key
intermediates
enable
an
intramolecular
1,5-HAT
intermolecular
HAT
process
for
nucleophilic
carbon-centered
radicals
formation
achieve
heteroarylation,
alkylation,
amination,
cyanation,
azidation,
trifluoromethylthiolation,
halogenation
deuteration.
value
this
protocol
is
further
demonstrated
by
gram-scale
synthesis
late-stage
natural
products
drug
derivatives.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(7), P. 2828 - 2832
Published: March 24, 2020
Here
we
report
a
method
for
the
site-selective
intermolecular
C(sp3)-H
amination
of
carboxamides
by
merging
transition-metal
catalysis
and
hydrogen
atom
transfer
strategy.
The
reaction
proceeds
through
sequence
favorable
single-electron
transfer,
1,5-hydrogen
C-N
cross-coupling
steps,
thus
allowing
access
to
series
desired
products.
This
could
accommodate
wide
diversity
nitrogen
nucleophiles
as
well
demonstrate
excellent
chemoselectivity
functional
group
compatibility.
