Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(3), С. 457 - 464
Опубликована: Дек. 9, 2023
An
arylation
of
anions
active
methylene
compounds
with
aryl
halides
provides
an
access
to
synthetically
versatile
α-arylated
1,3-diketones,
β-keto
esters,
nitriles,
β-cyano
etc.
Previously,
these
C−C
cross-coupling
reactions
have
been
accomplished
only
using
transition
metal-based
catalysts.
Herein,
we
demonstrate
that
arylations
can
be
successfully
realized
under
catalyst-free
conditions
employing
the
electron
donor-acceptor
(EDA)
complex
photoactivation
strategy.
The
protocol
was
further
optimized
for
a
semi-one
pot
synthesis
indole
derivatives
via
intramolecular
coupling.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1719 - 1737
Опубликована: Фев. 29, 2024
Abstract
Aryl
halides
are
one
of
the
most
important
chemical
feedstocks
in
pharmaceuticals
due
to
its
easy
accessibility,
inexpensiveness,
and
widely
utilized
as
aryl
radical
precursors
organic
synthetic
chemistry.
Conventionally,
stoichiometric
reagents
such
AIBN/n‐Bu
3
SnH
were
used
for
generation
from
halides,
suffered
requirement
toxic
initiators,
high
temperature
thus,
development
simple,
mild
strategies
highly
desirable.
Recently,
visible
light
mediated
received
considerable
attention,
allowing
under
reaction
conditions.
The
present
review
described
recent
breakthroughs
advancements
photocatalyst‐free
C−B/C/O/P/Se/S
bond
formation
halides.
Abstract
Visible‐light‐activated
organic
reactions
unlock
novel
avenues
for
complex
molecular
transformations,
impossible
under
standard
“thermal”
conditions,
which
makes
them
powerful
tools
in
the
arsenal
of
synthetic
chemistry.
However,
transition
metal‐based
or
photoredox
catalysts
are
often
used
to
ensure
productive
absorption
visible
light,
might
be
not
desirable
medicinal
chemistry
and
industry
due
toxicity,
low
sustainability,
high
cost
most
photocatalysts.
A
more
environmentally
economically
benign
approach
is
based
on
formation
transient
electron
donor‐acceptor
(EDA)
complexes
between
two
reagents
a
reagent
an
additive,
that
readily
absorb
acting
as
internal
photosensitizers.
Within
EDA
complex‐based
arylation
strategies,
chemical
transformations
mediated
by
noncovalent
interaction
molecules,
namely
electron‐poor
aryl
halides
their
equivalents
electron‐rich
nucleophilic
additives.
Moreover,
besides
stoichiometric
organocatalysis
can
achieved
certain
cases
through
regeneration
donor
molecules
course
reaction.
Photoexcitation
induces
single
transfer
(SET)
process
generate
radical
species
step.
This
Review
will
focus
state‐of‐the‐art
strategies
utilizing
halides,
aryldiazonium,
diaryliodonium,
arylsulfonium
arylphosphonium
salts
reactants,
published
mainly
last
five
years.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Heteroaromatic
alkylations
are
indispensable
reactions
for
synthesizing
biologically
active
molecules.
The
anti-Markovnikov
hydroarylation
of
olefins
using
heteroaryl
halides
furnishes
the
product
as
a
single
regioisomer;
however,
catalytic
variants
ineffective
at
controlling
stereochemical
outcome
these
reactions.
Here,
we
report
synergistic
photoenzymatic
flavin-dependent
"ene"-reductases
with
ruthenium
photoredox
catalysts.
Enzyme
homologues
were
identified,
which
provide
access
to
both
enantiomers
in
greater
than
80%
yield
up
99:1
er.
This
method
is
effective
styrenyl-
and
unactivated
alkenes,
highlighting
generality
this
approach.
highest
yielding
system
involves
carboxylated
photocatalyst
increased
affinity
enzyme.
work
expands
types
radical
intermediates
that
enzymes
can
use
stereoselective
intermolecular
coupling
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(14), С. 10096 - 10110
Опубликована: Июль 3, 2023
Herein
we
report
a
cascaded
chalcogenation
of
aryl
alkynoates
or
N-arylpropynamides
using
9-mesityl-10-methylacridinium
perchlorate
as
visible
light
photocatalyst
to
obtain
selectively
either
3-sulfenylated/selenylated
coumarins
spiro[4,5]trienones.
In
radical
initiated
process,
the
spiro-cyclization
reaction
was
favored
due
presence
-OMe
-F
substituent
at
para
position
group,
which
helped
stabilize
allylic
intermediate
formed
during
reaction.
Otherwise,
6-endo-trig
cyclization
led
coumarins.
Overall,
new
C–S/C–Se,
C–C,
and
C═O
bonds
were
in
single
step.
The
Stern–Volmer
quenching
study,
EPR
experiments,
ON-OFF
trapping
etc.,
understand
radical-based
mechanism.
Synthesis,
Год журнала:
2023,
Номер
55(10), С. 1467 - 1486
Опубликована: Фев. 27, 2023
Abstract
Use
of
sustainable
energy
sources
in
synthetic
organic
chemistry
has
become
one
the
most
popular
research
topics
due
to
environmental
pollution
and
global
warming.
In
this
review,
we
discuss
photocatalyst-free
transition-metal-free
light-induced
reactions
for
construction
carbon–carbon
(C–C)
bonds.
The
reaction
systems
discussed
here
are
C–C
bond
formation
via
carbene
intermediates,
radical
miscellaneous
cyclization.
1
Introduction
2
Bond
Formation
Carbene
Intermediates
3
Radical
4
Miscellaneous
Cyclization
5
Conclusion
Chemical Communications,
Год журнала:
2024,
Номер
60(21), С. 2926 - 2929
Опубликована: Янв. 1, 2024
This
article
introduces
a
catalyst-free
reductive
coupling
driven
by
visible-light,
facilitating
the
synthesis
of
pyridine-substituted
alcohols
and
amines
through
reaction
aldehydes,
ketones
imines
with
cyanopyridines.
Pure and Applied Chemistry,
Год журнала:
2023,
Номер
95(5), С. 465 - 474
Опубликована: Янв. 10, 2023
The
modern
synthetic
chemistry
heavily
relies
on
the
use
of
stoichiometric
organometallic
reagents
to
react
with
various
electrophiles.
dependence
quantities
metals
and
often
organic
halides
as
precursors,
in
turn
both
produces
copious
amounts
metal
halide
wastes
well
leads
concerns
future
sustainability.
Inspired
by
classical
Wolff-Kishner
reduction,
our
lab
has
recently
developed
a
general
strategy
Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(6), С. 102009 - 102009
Опубликована: Май 29, 2024
Toward
the
development
of
sustainable
resources,
degradation
lignin
presents
an
opportunity
for
valorization
biomass
into
valuable
chemicals
and
fuels.
In
this
study,
we
develop
approach
utilizing
2-bromo-anthraquinone
(2-Br-AQN)
as
a
green
cost-effective
organic
photocatalyst.
This
methodology
succeeds
in
degrading
six
different
sources
native
under
visible-light
conditions.
The
process
follows
redox-neutral
pathway,
eliminating
requirement
additional
oxidants,
bases,
transition
metals.
characteristic
enhances
environmental
friendliness
process,
making
it
more
sustainable.
Mechanistic
studies
density
functional
theory
(DFT)
calculations
suggest
that
reaction
involves
hydrogen-bond-promoted
proton-coupled
electron
transfer
(PCET)
process.
