Abstract
This
research
article
uses
density
functional
theory
(DFT)
to
study
photoinduced
borylation.
work
examined
the
electron
donor‐acceptor
complex
(EDA)
of
bis(catecholato)diboron
with
different
redox‐active
leaving
groups
and
bis(pinacol)diboron
aryl
N‐hydroxyphthalimide.
The
results
these
DFT
studies
show
ratio
B
2
cat
N,
N‐dimethylacetamide
(DMA)
should
be
1
:
which
is
consistent
experimental
in
literature.
We
further
proposed
a
reaction
mechanism
calculated
energies
associated
each
step.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(29)
Опубликована: Март 24, 2023
Abstract
The
photoactivation
of
electron
donor‐acceptor
complexes
has
emerged
as
a
sustainable,
selective
and
versatile
strategy
for
the
generation
radical
species.
Electron
(EDA)
complexation,
however,
imposes
electronic
constraints
on
donor
acceptor
components
this
can
limit
range
radicals
that
be
generated
using
approach.
New
EDA
complexation
strategies
exploiting
sulfonium
salts
allow
to
from
native
functionality.
For
example,
aryl
salts,
formed
by
activation
arenes,
serve
in
due
their
electron‐deficient
nature.
This
“sulfonium
tag”
approach
relaxes
parent
substrate
dramatically
expands
complexation.
In
review,
these
new
applications
will
introduced
areas
chemical
space
rendered
accessible
through
innovation
highlighted.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(43)
Опубликована: Сен. 13, 2023
Abstract
The
utilization
of
aryl
radicals
as
open‐shelled
intermediates
has
become
an
essential
tool
for
both
conventional
and
state‐of‐the‐art
synthetic
chemistry.
However,
the
current
methods
generating
are
still
inefficient,
greatly
impeding
their
practical
applications.
Encouragingly,
sulfonium
salts
have
emerged
appealing
sources
a
wide
range
transformations
aimed
at
creating
novel
chemical
bonds
driven
by
distinctive
structural
attributes
tendencies.
This
review
primarily
focuses
on
specific
reaction
mechanisms
underlying
cleavage
C−S
in
salts,
leading
to
generation
corresponding
within
diverse
conditions.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(16), С. 1979 - 1986
Опубликована: Апрель 5, 2023
Comprehensive
Summary
A
novel
transient
SET
mediator
approach
has
been
developed
for
the
photoinduced
radical‐radical
cross
coupling
reaction.
Using
in‐situ
generated
thianthrene
radical
cation
as
mediator,
thiocyanation
and
selenocyanation
of
aryl
thianthrenium
salts
have
realized
under
mild
conditions
without
need
photocatalyst
or
single
electron
donor.
In
comparison
with
enabled
process,
protocol
features
conditions,
simple
manipulation,
a
broad
substrate
scope,
excellent
functional
group
heterocycle
tolerance.
Due
to
feasible
accessibility
salts,
this
method
also
applied
in
efficient
synthesis
bioactive
molecule,
late‐stage
functionalization
complex
arenes.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(31)
Опубликована: Март 28, 2024
Abstract
Photoinduced
aryl
radical
generation
is
a
powerful
strategy
in
organic
synthesis
that
facilitates
the
formation
of
diverse
carbon‐carbon
and
carbon‐heteroatom
bonds.
The
synthetic
applications
photoinduced
complex
compounds,
including
natural
products,
physiologically
significant
molecules,
functional
materials,
have
received
immense
attention.
An
overview
current
developments
production
methods
their
uses
given
this
article.
A
generalized
idea
how
to
choose
reagents
approach
for
radicals
described,
along
with
techniques
associated
mechanistic
insights.
Overall,
article
offers
critical
assessment
results
as
well
selection
reaction
parameters
specific
context
cascades,
cross‐coupling
reactions,
functionalization,
selective
C−H
functionalization
substrates.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5227 - 5235
Опубликована: Март 21, 2024
Sulfonamides
are
prominently
featured
in
organic
synthesis
and
medicinal
chemistry.
Yet,
a
general
synthetic
platform
for
the
modular
construction
of
aryl
sulfonamides
remains
elusive.
Herein,
metal-free
photoredox-catalyzed
three-component
via
an
sulfonyl
ammonium
salt
intermediate,
which
was
generated
situ
SET
event,
has
been
established.
A
variety
structurally
diverse
primary,
secondary,
tertiary
were
synthesized
rapidly
from
abundant
amines
or
sodium
azide
under
mild
conditions.
Notably,
primary
aliphatic
amine,
challenging
Cu-catalyzed
protocols,
worked
well
this
approach.
Moreover,
fluoride
can
be
accessed
smoothly
as
well,
using
potassium
hydrogen
nucleophile.
The
potential
utility
conversion
is
demonstrated
facile
three
bioactive
drug
compounds.
Preliminary
mechanistic
studies
have
revealed
that
radical
key
intermediates
mechanistically
innovative
methodology.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 16, 2024
The
advancement
in
electrochemical
techniques
has
unlocked
a
new
path
for
achieving
unprecedented
oxidations
and
reductions
of
aryl
radical
precursors
controlled
selective
manner.
This
approach
facilitates
the
construction
aromatic
carbon-carbon
carbon-heteroatom
bonds.
In
light
green
merits
growing
importance
this
technique
chemistry,
review
aims
to
provide
an
overview
recent
advance
generation
radicals
organized
by
precursor
type,
with
focus
on
substrate
scope,
limitation,
underlying
mechanism,
thereby
inspiring
future
work
generation.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(12)
Опубликована: Фев. 13, 2023
Abstract
Organoboron
compounds
are
versatile
synthons
in
synthetic
chemistry,
materials
science,
and
medicinal
chemistry.
The
preparation
of
them
often
requires
either
reactive
organometallic
reagents
or
transition
metals.
In
recent
years,
transition‐metal‐free
borylation
methodologies
using
radical
chemistry
for
C−B
bond
formation
have
attracted
much
attention
developed
rapidly,
which
circumvents
the
use
preformed
reagents.
Various
successful
approaches
from
different
precursors
(such
as
carboxylic
acids,
amines
alcohols,
abundant
nature)
through
thermochemical,
photochemical
electrochemical
pathways
been
developed.
Therefore,
this
review,
we
hope
to
provide
an
overview
advances
discovery,
development,
mechanistic
study
processes.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 8, 2024
Aryl
thianthrenium
salts
are
valuable
in
photocatalysis
but
traditionally
require
external
electron
donors
for
activation.
This
study
introduces
an
energy
transfer
(EnT)
strategy
the
activation
of
aryl
using
2,3,4,5,6-penta(carbazol-9-yl)benzonitrile
(5CzBN)
as
a
metal-free
photocatalyst,
eliminating
need
donors.
Utilizing
this
EnT
approach,
we
achieve
C-H
deuteration
arenes
under
visible
light
with
CDCl