Angewandte Chemie,
Год журнала:
2024,
Номер
136(26)
Опубликована: Апрель 17, 2024
Abstract
The
construction
of
C(sp
3
)−N
bonds
via
direct
N‐centered
radical
addition
with
olefins
under
benign
conditions
is
a
desirable
but
challenging
strategy.
Herein,
we
describe
an
organo‐photocatalytic
approach
to
achieve
anti‐Markovnikov
alkene
hydroamidation
sulfonyl
azides
in
highly
efficient
manner
transition‐metal‐free
and
mild
conditions.
A
broad
range
substrates,
including
both
activated
unactivated
alkenes,
are
suitable
for
this
protocol,
providing
convenient
practical
method
construct
sulfonylamide
derivatives.
synergistic
experimental
computational
mechanistic
study
suggests
that
the
additive,
Hantzsch
ester
(
HE
),
might
undergo
triplet‐triplet
energy
transfer
photosensitization
by
organo‐photocatalyst
visible
light
irradiation.
Next,
resulted
triplet
excited
state
*
could
lead
homolytic
cleavage
C
4
−H
bond,
which
triggers
straightforward
H‐atom
(HAT)
style
converting
azide
corresponding
key
amidyl
radical.
Subsequently,
followed
HAT
from
p
‐toluenethiol
proceed
afford
desired
product.
It
worth
noting
pathway
bifurcation
be
possible
reaction.
feasible
chain
propagation
also
proposed
rationalize
high
efficiency
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
10(1), С. 216 - 236
Опубликована: Ноя. 8, 2022
The
late
stage
functionalization
(LSF)
is
a
distinctive
approach
for
accelerating
the
discovery
of
structure–activity
relationships
(SARs)
and
optimising
ADME
(absorption,
distribution,
metabolism,
excretion)
profiles.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 25, 2022
Herein,
a
copper(I)-catalyzed
reaction
of
diarylphosphines
and
O-benzoyl
hydroxylamines
is
developed.
In
the
cases
symmetrical
diarylphosphines,
series
aminophosphinites
prepared
in
high
yields.
unsymmetrical
an
array
P-chiral
synthesized
yields
with
enantioselectivity
by
using
copper(I)-(R,RP
)-Ph-FOXAP
complex
as
chiral
catalyst.
Based
on
several
control
experiments
31
P
NMR
studies,
two-electron
redox
mechanism
involving
dynamic
kinetic
asymmetric
transformation
proposed
for
reaction.
Finally,
one
representative
phosphoric
amide
generated
through
oxidation
H2
O2
transformed
to
diarylphosphinate
yield
retained
enantioselectivity,
which
allows
further
transformations
towards
various
tertiary
phosphines.
ACS Catalysis,
Год журнала:
2021,
Номер
11(9), С. 5026 - 5034
Опубликована: Апрель 9, 2021
The
construction
of
C(sp3)–N
bonds
via
direct
radical–radical
cross-coupling
under
benign
conditions
is
a
desirable
but
challenging
approach.
Herein,
the
alkyl
and
amidyl
radicals
to
build
aliphatic
C–N
in
concise,
mild,
oxidant-free
manner
implemented
by
nickel/photoredox
dual
catalysis.
In
this
protocol,
single
electron
transfer
strategy
successfully
employed
generate
N-
C-centered
from
sulfonyl
azides/azidoformates
alkyltrifluoroborates,
respectively.
photocatalyst-induced
triplet–triplet
energy-transfer
mechanism,
however,
might
not
be
applicable
reaction.
oxidative
quenching
pathway
excited
photocatalyst
(RuII/*RuII/RuIII/RuII)
combined
with
possible
NiI/NiII/NiIII/NiI
catalytic
cycle
proposed
account
for
dual-catalyzed
bond
formation
based
on
synergistic
experimental
computational
studies.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1559 - 1564
Опубликована: Фев. 14, 2024
Abstract
A
photoredox/copper
co‐catalyzed
ring‐opening
cross‐coupling
of
aryl
azides
with
cyclopropanols
has
been
developed
fac
‐Ir(ppy)
3
as
the
photocatalyst.
The
reaction
involves
intermediacy
anilino
radical
generated
through
reduction
azido
group
by
*
and
[Cu
II
]‐enabled
oxidative
cyclopropanol.
An
array
β‐aminoketone
compounds
were
synthesized
under
redox‐neutral
conditions
using
this
method.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7848 - 7858
Опубликована: Май 29, 2024
A
CuH-catalyzed
reductive
coupling
of
nitroarenes
with
phosphine
oxides
is
developed,
which
produces
a
series
phosphamides
in
moderate
to
excellent
yields
good
functional
group
tolerance.
Gram-scale
synthesis
and
late-stage
modification
nitro-aromatic
molecule
niclosamide
are
also
successfully
conducted.
The
mechanism
study
shows
that
the
nitro
transformed
after
being
reduced
nitroso
nucleophilic
addition
procedure
involved
during
reaction.
Organic Letters,
Год журнала:
2023,
Номер
25(15), С. 2555 - 2559
Опубликована: Март 6, 2023
Phosphoranyl
radicals
are
essential
mediators
to
bring
about
new
but
often
produce
a
stoichiometric
amount
of
phosphine
oxide/sulfide
waste.
Herein,
we
devised
phosphorus-containing
species
as
radical
precursor,
without
the
generation
phosphorus
Accordingly,
catalyst-free
synthesis
phosphinic
amides
from
hydroxyl
amines
and
chlorophosphines
via
P(III)
P(V)
rearrangement
is
described.
Mechanistically,
it
may
involve
initial
formation
R2N-O-PR2
that
undergoes
homolysis
N-O
bonds
subsequent
recombination.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(9), С. 6224 - 6236
Опубликована: Апрель 20, 2022
An
efficient
copper-catalyzed
aerobic
oxidative
cross-dehydrogenative
coupling
reaction
for
the
synthesis
of
multisubstituted
phosphorylhydrazides
from
N,N-disubstituted
hydrazines
and
hydrogen
phosphoryl
compounds
is
accomplished.
The
proceeds
under
mild
conditions
without
addition
any
external
oxidants
bases.
This
work
reported
here
represents
a
direct
P(═O)-N-N
bond
formation
with
advantages
being
operationally
simple,
good
functional
group
tolerance,
high
atom
step
economy.
Furthermore,
selected
exhibit
potential
inhibitory
activity
against
tumor
cells,
which
can
be
used
in
field
screening
anticancer
agents
as
new
chemical
entities.
