Organophosphorus
aza-heterocycles
are
widely
found
in
the
framework
of
bioactive
molecules,
materials,
and
commercially
available
medications.
We
report
a
photoredox-catalyzed
cascade
radical
addition/annulation
sequences
acyclic
phosphinimides
with
organohalides
under
mild
external
oxidant-free
reaction
conditions.
A
wide
range
functionalized
bearing
quaternary
carbon
center
can
be
efficiently
selectively
produced
by
employing
diverse
precursors,
which
including
sulfonyl,
perfluoroalkyl,
trichloromethyl,
carbonyl
halides,
respectively.
Green Chemistry,
Год журнала:
2024,
Номер
26(12), С. 7331 - 7336
Опубликована: Янв. 1, 2024
A
novel
photocatalytic
acylation
strategy
was
developed
harnessing
tetrabutylammonium
decatungstate
(TBADT)
as
a
hydrogen
atom
transfer
(HAT)
photocatalyst
to
facilitate
the
direct
coupling
of
aldehydes
with
N-heterocycles
at
ambient
temperature.
Chemical Reviews,
Год журнала:
2024,
Номер
124(17), С. 10192 - 10280
Опубликована: Авг. 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
Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(21), С. 3053 - 3064
Опубликована: Окт. 11, 2023
ConspectusThe
development
of
functionalization
reactions
involving
the
activation
C-H
bonds
has
evolved
extensively
due
to
atom
and
step
economy
associated
with
such
reactions.
Among
these
reactions,
chelation
assistance
been
shown
provide
a
powerful
solution
serious
issues
reactivity
regioselectivity
faced
in
bonds.
The
vast
majority
reported
thus
far
involved
use
precious
metals.
Kleiman
Dubeck
cyclonickelation
azobenzene
NiCp2
which
an
azo
group
directs
Ni
center
activate
ortho
bond
close
proximity.
Although
this
stoichiometric
reaction
was
discovered
earlier
than
that
for
other
transition-metal
complexes,
its
as
catalytic
delayed.
No
general
systems
were
available
Ni-catalyzed
long
time.
This
Account
details
our
group's
Ni(0)-
Ni(II)-catalyzed
chelation-assisted
It
also
highlights
how
new
strategy
can
be
extended
unreactive
bonds.In
early
2010s,
we
found
Ni(0)-catalyzed
aromatic
amides
contain
2-pyridinylmethylamine
moiety
directing
alkynes
results
C-H/N-H
oxidative
annulation
give
isoquinolinones.
In
addition,
combination
Ni(II)
catalyst
8-aminoquinoline
superior
developing
wide
variety
various
electrophiles.
proposed
include
formation
unstable
Ni(IV)
and/or
Ni(III)
species;
generation
high-valence
species
rare
at
time,
but
since
then,
many
papers
dealing
DFT
organometallic
studies
have
appeared
literature
attempts
understand
mechanism.
Based
on
in-depth
considerations
mechanism
respect
why
N,N-bidentate
is
required,
realized
N-Ni
by
addition
N-H
Ni(0)
or
ligand
exchange
between
key
step.
We
concluded
precoordination
N(sp2)
positions
proximity
permits
bond.
working
hypothesis,
carried
out
using
KOtBu
base
do
not
specific
desired
isoquinolinone,
amidate
anion
acts
actual
group.
Remarkably,
applicable
C-F,
C-O,
C-S,
C-CN.
Chemical Science,
Год журнала:
2024,
Номер
15(20), С. 7707 - 7713
Опубликована: Янв. 1, 2024
By
leveraging
the
synergistic
interplay
between
nickel
and
photoredox
catalysis,
we
have
developed
a
three-component
silylacylation
strategy
for
various
acrylates,
yielding
valuable
building
blocks
with
carbonyl
silicon
functionalities.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7009 - 7013
Опубликована: Сен. 14, 2023
The
1,2-iminylalkylation
of
diazenes
using
alkyl
iodides
in
combination
with
an
O-benzoyl
oxime
is
reported.
In
this
transformation,
acted
as
a
radical
precursor
and
XAT
mediator.
addition
to
common
iodides,
other
such
iodomethane,
iodomethane-d3,
trifluoroiodomethane,
ethyl
difluoroiodoacetate,
iodoalkanes
containing
unprotected
hydroxyl
amide
groups
can
also
serve
C-radical
precursors
the
electrophilic
acceptors.
Molecules,
Год журнала:
2025,
Номер
30(8), С. 1711 - 1711
Опубликована: Апрель 11, 2025
Traditionally
employed
as
hydrogenation
reagents,
benzothiazolines
have
emerged
versatile
carbanion
and
radical
transfer
playing
a
vital
role
in
the
construction
of
various
carbon-carbon
bonds.
The
cutting-edge
progress
photochemistry
chemistry
prompted
study
visible
light-driven
reactions,
bringing
into
vibrant
focus.
Their
chemical
processes
been
uncovered
to
encompass
variety
activation
mechanisms,
with
five
distinct
modes
having
identified.
This
work
reviews
innovative
applications
donors
alkyl
or
acyl
groups,
achieving
hydroalkylation
hydroacylation
substitution.
By
examining
their
diverse
this
review
highlights
potential
serving
groups
for
further
research
development.
Moreover,
will
offer
exemplary
inspiration
synthetic
chemists,
contributing
ongoing
evolution
utility
organic
synthesis.
Synthesis,
Год журнала:
2024,
Номер
56(16), С. 2558 - 2564
Опубликована: Май 23, 2024
Abstract
A
dual
cobalt
and
chromium
photoredox-catalyzed
allylation
of
aldehydes
with
allenes
through
a
photo
metal-hydride
atom
transfer
(MHAT)
process
has
been
developed
to
yield
homoallylic
alcohols
exceptional
diastereoselective
control.
This
sustainable
efficient
method
holds
significant
promise
for
applications
in
the
synthesis
valuable
organic
compounds.
Green Synthesis and Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 1, 2024
Organophosphorus
aza-heterocycles
are
widely
found
in
the
framework
of
numerous
bioactive
molecules,
functional
materials,
and
commercially
available
drugs.
We
report
herein
a
photoredox-catalyzed
radical
addition
cascade
annulation
sequence
acyclic
phosphinimides
with
variety
organohalides
under
mild
external
oxidant-free
reaction
conditions.
A
wide
range
functionalized
bearing
quaternary
carbon
center
could
be
efficiently
selectively
produced
by
employing
diverse
precursors,
including
sulfonyl,
perfluoroalkyl,
trichloromethyl,
carbonyl
halides,
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(30), С. 13801 - 13806
Опубликована: Июль 17, 2024
This
computational
study
revises
and
reformulates
the
mechanism
for
cross-coupling
reaction
between
chlorobenzene
tetrahydrofuran
catalyzed
by
a
Ni
complex
with
assistance
of
an
Ir
photocatalyst.
is
representative
process
transition-metal
photocatalysis,
variations
it
have
been
reported
different
experimental
authors.
It
has
also
subject
previous
studies,
which
we
revise
extend.
Density
functional
theory
(DFT)
calculations
microkinetic
modeling
indicate
that
most
efficient
takes
place
through
energy-transfer
step
involves
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 27, 2024
Tetrahydropyridazines
constitute
an
important
structural
motif
found
in
numerous
natural
products
and
pharmaceutical
compounds.
Herein,
we
report
aminoacylation
reaction
of
alkenes
that
enables
the
synthesis
1,4,5,6-tetrahydropyridazines
through
cooperative
N-heterocyclic
carbene
(NHC)
photoredox
catalysis.
This
approach
involves
6-endo-trig
cyclization
N-centered
hydrazonyl
radicals,
generated
via
single-electron
oxidation
hydrazones,
followed
by
a
radical-radical
coupling
step.
The
mild
process
tolerates
wide
range
common
functional
groups
affords
variety
tetrahydropyridazines
moderate
to
high
yields.
Preliminary
investigations
using
chiral
NHC
catalysts
demonstrate
potential
this
protocol
for
asymmetric
radical
reactions.
