Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(45), P. 13140 - 13150
Published: Jan. 1, 2023
Transition
metal-based
charge-transfer
complexes
represent
a
broad
class
of
inorganic
compounds
with
diverse
photochemical
applications.
Charge-transfer
based
on
earth-abundant
elements
have
been
increasing
interest,
particularly
the
canonical
[Fe(bpy)3]2+.
Photoexcitation
into
singlet
metal-ligand
charge
transfer
(1MLCT)
state
is
followed
by
relaxation
first
to
ligand-field
manifold
and
then
ground
state.
While
these
dynamics
well-studied,
processes
within
MLCT
that
facilitate
and/or
compete
more
elusive.
We
applied
ultrafast
two-dimensional
electronic
spectroscopy
(2DES)
disentangle
immediately
following
excitation
this
compound.
First,
ascribed
out
initially
formed
1MLCT
was
found
correlate
inertial
response
time
solvent.
Second,
additional
dimension
2D
spectra
revealed
peak
consistent
∼20
fs
→
3MLCT
intersystem
crossing
process.
These
two
observations
indicate
complex
simultaneously
undergoes
direct
conversion
state(s).
Resolution
parallel
pathways
in
prototypical
highlights
ability
2DES
deconvolve
otherwise
obscured
excited-state
complexes.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Aug. 26, 2022
Abstract
The
merger
of
photoredox
and
transition-metal
catalysis
has
evolved
as
a
robust
platform
in
organic
synthesis
over
the
past
decade.
stereoselective
1,4-functionalization
1,3-enynes,
prevalent
synthon
synthetic
chemistry,
could
afford
valuable
chiral
allene
derivatives.
However,
tremendous
efforts
have
been
focused
on
ionic
reaction
pathway.
radical-involved
asymmetric
1,3-enynes
remains
prominent
challenge.
Herein,
we
describe
three-component
1,4-dialkylation
via
dual
chromium
to
provide
allenols.
This
method
features
readily
available
starting
materials,
broad
substrate
scope,
good
functional
group
compatibility,
high
regioselectivity,
simultaneous
control
axial
central
chiralities.
Mechanistic
studies
suggest
that
this
proceeds
through
redox-neutral
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(32), P. 6018 - 6023
Published: Aug. 10, 2022
We
disclosed
herein
a
straightforward
photochemical
method
for
the
construction
of
phenanthridines
containing
synthetically
useful
succinate
unit.
The
reaction
occurred
under
visible-light
irradiation
with
cheap
eosin
Y
Na
as
photoredox
catalyst
and
diazo
compound
precursor.
Under
optimal
conditions,
wide
range
were
obtained
in
moderate
to
good
yields.
Note
that
units
final
heterocycles
could
be
easily
transformed
into
many
valuable
structures,
such
γ-butyrolactone,
dihydrofuran-2(3H)-one,
tetrahydrofuran.
Mechanistic
experiments
performed
support
proposed
mechanism.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2023,
Volume and Issue:
11(3), P. 910 - 920
Published: Jan. 11, 2023
The
first
piezochemically
driven
decarboxylative
coupling
of
the
C–H
bond
was
developed.
agitation
BaTiO3
via
ball
milling
converts
mechanical
energy
into
electrical
potential,
leading
to
production
a
benzoyl
radical
single-electron
transfer
pathway
analogous
photocatalytic
reaction.
This
mechanoredox
catalytic
strategy
synthesize
C3-acylated
quinoxalin-2(1H)-ones
requires
no
solvent,
short
reaction
time,
and
simple
handling
skills,
exhibiting
promising
potential
in
large-scale
chemical
manufacturing.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(18), P. 4488 - 4515
Published: Jan. 1, 2023
This
review
highlights
the
recent
advances
in
radical
acylated
difunctionalization
of
unsaturated
carbon–carbon
bonds
and
focuses
on
mechanistic
insights
these
transformations.
ACS Central Science,
Journal Year:
2023,
Volume and Issue:
9(4), P. 756 - 762
Published: March 27, 2023
Direct
functionalization
of
inert
C-H
bonds
is
one
the
most
attractive
yet
challenging
strategies
for
constructing
molecules
in
organic
chemistry.
Herein,
we
disclose
an
unprecedented
and
Earth
abundant
Cu/Cr
catalytic
system
which
unreactive
alkyl
are
transformed
into
nucleophilic
alkyl-Cr(III)
species
at
room
temperature,
enabling
carbonyl
addition
reactions
with
strong
bonds.
Various
aryl
alcohols
furnished
under
mild
reaction
conditions
even
on
a
gram
scale.
Moreover,
this
new
radical-to-polar
crossover
approach
further
applied
to
1,1-difunctionalization
aldehydes
alkanes
different
nucleophiles.
Mechanistic
investigations
reveal
that
aldehyde
not
only
acts
as
reactant
but
also
serves
photosensitizer
recycle
Cu
Cr
catalysts.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(23), P. 3419 - 3432
Published: July 27, 2023
Comprehensive
Summary
Transition
metal‐catalyzed
carbonylation
reactions
represent
a
direct
and
atom‐economical
approach
to
synthesize
carbonyl
compounds
or
their
derivatives
by
using
CO
as
cheap
readily
available
C1
feedstock.
While
of
C(sp
2
)‐hybridized
electrophiles
(
e.g
.,
aryl
halides)
is
well
developed,
less
reactive
unactivated
alkyl
remains
challenging.
Recently,
the
use
earth‐abundant
base
metals
including
Cu,
Co,
Mn,
Fe,
Ni
catalysts
has
enabled
advances
in
carbonylative
coupling
for
approaching
diverse
derivatives,
notably,
some
which
are
synthetic
importance
but
difficult
be
synthesized
through
previous
reported
methods.
Herein,
we
have
summarized
discussed
these
recent
achievements
base‐metal‐catalyzed
C—C,
C—N,
C—O,
C—X
other
source.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
16(10), P. 4442 - 4449
Published: Jan. 1, 2025
Catalytic
methods
by
switching
the
least
parameters
for
regioselective
and
site-divergent
transformations
to
construct
different
architectures
from
identical
readily
available
starting
materials
are
among
most
ideal
catalytic
protocols.
However,
associated
challenge
precisely
control
both
regioselectivity
site
diversity
renders
this
strategy
appealing
yet
challenging.
Herein,
Ni-catalyzed
cross-electrophile
1,2-
1,3-arylalkylations
of
N-acyl
allylic
amines
have
been
developed.
This
reductive
three-component
protocol
enables
1,2-arylalkylation
1,3-arylalkylation
with
aryl
halides
alkyl
excellent
chemo-,
regio-
site-selectivity,
representing
first
example
controlled
migratory
difunctionalization
alkenes
under
conditions.
A
wide
range
terminal
internal
unactivated
amines,
precursors
were
tolerated,
providing
straightforward
efficient
access
diverse
C(sp3)-rich
branched
aliphatic
materials.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(31), P. 5710 - 5714
Published: Aug. 3, 2022
An
intermolecular
1,2-diacylation
of
alkenes
is
disclosed
via
cooperative
N-heterocyclic
carbene
and
photoredox
catalysis
under
the
mediation
PPh3
Cs2CO3.
This
protocol
provides
a
practical
approach
for
construction
1,4-dicarbonyl
compounds
toward
novel
diketone
pharmaceutical
derivatives.
Furthermore,
regioselective
dicarbonyl
can
be
synthesized
by
adding
acyl
azolium
salt.
Mechanistic
investigations
suggest
that
process
was
critical
radical/radical
cross
coupling
ketyl
radicals
with
benzylic
C-radicals.