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.
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
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(5), С. 1412 - 1419
Опубликована: Янв. 1, 2024
Herein,
we
developed
a
photo-induced
1,2-alkylarylation
and
cyclization
of
alkenes,
alkyl
halides
N
-alkylindoles
to
synthesize
indoles
derivatives
polysubstituted
tetrahydrofuran
under
mild
conditions
without
the
use
external
redox
reagents
photosensitizers.
Green Chemistry,
Год журнала:
2024,
Номер
26(8), С. 4518 - 4527
Опубликована: Янв. 1, 2024
The
selection
of
electronically-different
thiolate-based
photosensitizers
is
employed
to
achieve
a
precise
and
specific
C–F
bond
defluorination
broad
range
trifluoromethylarenes,
enabling
the
synthesis
88
α,α-difluoromethyl
compounds.
