Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(14), P. 2738 - 2743
Published: March 31, 2022
The
free
radical
cyclization
reaction
is
a
promising
strategy
for
ring
framework
formation.
Herein,
we
report
copper-catalyzed
tandem
preparing
substituted
lactam
derivatives.
This
proceeds
through
coupling
approach,
which
not
only
allows
wide
range
of
alkenes
but
also
quite
compatible
with
the
primary,
secondary,
and
tertiary
radicals.
In
addition,
density
functional
theory
calculations
were
performed
to
gain
insights
into
mechanism.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(20), P. 10967 - 10973
Published: April 19, 2023
Despite
the
widespread
applications
of
α-hydroxyalkyl
cyclic
amines,
direct
and
diverse
access
to
such
a
class
unique
vicinal
amino
alcohols
still
remains,
date,
challenge.
Here,
through
strategy
electroreductive
α-hydroxyalkylation
inactive
N-heteroarenes
with
ketones
or
electron-rich
arylaldehydes,
we
describe
room
temperature
approach
for
construction
which
features
broad
substrate
scope,
operational
simplicity,
high
chemoselectivity,
no
need
pressurized
H2
gas
transition
metal
catalysts.
The
zinc
ion
generated
from
anode
oxidation
plays
crucial
role
in
activation
both
reactants
by
decreasing
their
reduction
potentials.
electroreduction
combination
Lewis
acids
this
work
is
anticipated
develop
more
useful
transformations.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 5491 - 5502
Published: March 28, 2024
Amino
acid
esters
serve
as
crucial
intermediates
in
protein
synthesis
and
common
structural
elements
biologically
active
natural
compounds.
Herein,
we
present
an
efficient
radical
cascade
reaction
involving
1,2-nitrogen
migration
C(sp2)–H
intramolecular
cyclization,
enabling
access
to
a
diverse
array
of
β-amino
motifs.
Upon
cooperative
Ni/diboron
catalysis,
π-system-independent
1,2-N-shift
β-bromo
α-amino
is
achieved,
which
allows
the
formation
two
new
bonds,
including
C(sp3)–C(sp2)
bond
C(sp3)–N
bond.
The
exhibits
extensive
substrate
compatibility
high
diastereoselectivity
proceeds
without
need
for
oxidants,
toxic
initiators,
and/or
elevated
temperatures.
It
has
been
observed
that
diboron
compounds
both
activating
reagent
inert
C–N
cleavage/migration
reductant
Ni
catalytic
cycle.
This
sheds
light
on
remote
N-functionalities
π-systems.
cascades
followed
by
intermolecular
halogenation
or
selenation
are
also
demonstrated.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(32), P. 17527 - 17550
Published: Aug. 2, 2023
The
C–O
bond
is
ubiquitous
in
biologically
active
molecules,
pharmaceutical
agents,
and
functional
materials,
thereby
making
it
an
important
group.
Consequently,
the
development
of
bond-forming
reactions
using
catalytic
strategies
has
become
increasingly
research
topic
organic
synthesis
because
more
conventional
methods
involving
strong
base
acid
have
many
limitations.
In
contrast
to
ionic-pathway-based
methods,
copper-promoted
radical-mediated
formation
experiencing
a
surge
interest
owing
renaissance
free-radical
chemistry
photoredox
catalysis.
This
Perspective
highlights
appraises
state-of-the-art
techniques
this
burgeoning
field.
contents
are
organized
according
different
reaction
types
working
models.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(47), P. 8451 - 8456
Published: Nov. 16, 2023
The
three-component
reactions
of
enaminones,
disulfides,
and
alcohols
for
the
synthesis
polyfunctionalized
alkenes
have
been
realized
via
C-H
C-N
bond
transformation
on
enaminones.
proceed
in
a
novel
"alkene-to-alkene"
difunctionalization
mode
without
using
any
transition
metal.
application
alkene
products
divergent
sulfenyl
heteroaryls,
including
sulfenylated
pyrazoles,
pyrimidines,
isoxazoles,
simple
annulation
has
also
verified.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3115 - 3127
Published: Feb. 13, 2024
Although
the
transition
metal-catalyzed
radical
fluorine
atom
transfer
(FAT)
strategy
has
emerged
as
a
powerful
tool
for
construction
of
C–F
bonds,
to
our
knowledge,
this
approach
rarely
been
applied
formation
S–F
bonds.
Here,
we
report
that
4-methoxypyridine
1-oxide
can
serve
an
inexpensive
and
simple
yet
effective
ligand
thus
promote
transformation
copper-mediated
challengeable
FAT
sulfonyl
radicals,
paving
way
assembly
FSO2
group.
Based
on
concept,
three
Cu(I)-catalyzed
protocols
involving
site-selective
intra-
intermolecular
fluorosulfonylation
inert
C(sp3)–H
bonds
1,2-aminofluorosulfonylation
inactivated
alkenes
have
developed,
enabling
preparation
C(sp3)-rich
aliphatic
fluorides
cannot
be
easily
synthesized
by
known
methods.
These
practical
operationally
methods
result
in
high
functional
group
tolerance
under
mild
conditions
modification
bioactive
derivatives
highly
valued
molecules.
Detailed
mechanistic
studies
indicate
unique
role
facilitating
such
rare
FATs
via
outer-sphere
pathway.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(17), P. 10192 - 10280
Published: Aug. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2440 - 2444
Published: March 19, 2024
An
iodoarene-driven
electroreductive
remote
C(sp3)–H
arylation
of
unsymmetrical
1-(o-iodoaryl)alkyl
ethers
with
cyanoarenes
for
the
site
selective
synthesis
α-(hetero)aryl
is
developed.
With
introduction
as
both
aryl
sources
and
electron
transfer
mediators,
this
method
includes
an
strategy
to
enable
regiocontrollable
formation
two
new
bonds,
one
C(sp2)–H
bond,
C(sp2)–C(sp3)
in
a
single
reaction
step
through
sequence
halogen
atom
(XAT),
hydrogen
(HAT),
radical–radical
coupling,
decyanation.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(2), P. 1667 - 1676
Published: Jan. 7, 2025
We
report
a
Ni-catalyzed
vicinal
alkylarylation
of
unactivated
alkenes
in
γ,δ-
and
δ,ε-alkenylamines
with
aryl
halides
alkylzinc
reagents.
The
reaction
is
enabled
by
amine
coordination
can
use
all
primary,
secondary,
tertiary
amines.
constructs
two
new
C(sp3)-C(sp3)
C(sp3)-C(sp2)
bonds
produces
δ-
ε-arylamines
C(sp3)-branching
at
the
γ-
δ-positions.
A
variety
heteroaryl
iodides
both
primary
secondary
reagents
be
used
as
coupling
carbon
sources.
Mechanistic
studies
suggest
that
cooperative
effect
organic
nitriles
electron-deficient
(EDAs)
ligands.