The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
Despite
the
widespread
ortho-functionalization
of
cyclic
diaryliodoniums
in
organic
chemistry,
corresponding
meta-functionalization
is
less
explored.
Herein,
we
report
a
practical
meta-selective
activation
hypervalent
iodoniums
for
synthesis
4-amino
coumarin
derivatives
broad
functional
group
tolerance
and
environmentally
friendly
manner.
The
practicability
this
protocol
was
further
highlighted
by
late-stage
modification
some
common
pharmaceuticals
natural
products.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(4), P. 1364 - 1416
Published: Jan. 17, 2023
Hypervalent
aryliodoumiums
are
intensively
investigated
as
arylating
agents.
They
excellent
surrogates
to
aryl
halides,
and
moreover
they
exhibit
better
reactivity,
which
allows
the
corresponding
arylation
reactions
be
performed
under
mild
conditions.
In
past
decades,
acyclic
aryliodoniums
widely
explored
However,
unmet
need
for
is
improvement
of
their
notoriously
low
reaction
economy
because
coproduced
iodides
during
often
wasted.
Cyclic
have
intrinsic
advantage
in
terms
economy,
started
receive
considerable
attention
due
valuable
synthetic
applications
initiate
cascade
reactions,
can
enable
construction
complex
structures,
including
polycycles
with
potential
pharmaceutical
functional
properties.
Here,
we
summarizing
recent
advances
made
research
field
cyclic
aryliodoniums,
nascent
design
aryliodonium
species
applications.
First,
general
preparation
typical
diphenyl
iodoniums
described,
followed
by
heterocyclic
monoaryl
iodoniums.
Then,
initiated
arylations
coupled
subsequent
domino
summarized
construct
polycycles.
Meanwhile,
building
biaryls
axial
atropisomers
discussed
a
systematic
manner.
Finally,
very
advance
employed
halogen-bonding
organocatalysts
described.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(31)
Published: May 11, 2024
The
use
of
noncovalent
interactions
based
on
electrophilic
halogen,
chalcogen,
pnictogen,
or
tetrel
centers
in
organocatalysis
has
gained
noticeable
attention.
Herein,
we
provide
an
overview
the
most
important
developments
last
years
with
a
clear
focus
experimental
studies
and
catalysts
which
act
via
such
non-transient
interactions.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(48), P. 5880 - 5896
Published: Jan. 1, 2021
Chemical
reactions
are
ubiquitous
in
the
universe,
they
at
core
of
life,
and
essential
for
industrial
processes.
The
drive
a
deep
understanding
how
something
occurs,
this
case,
mechanism
chemical
reaction
factors
controlling
its
reactivity,
is
intrinsically
valuable
an
innate
quality
humans.
level
insight
degree
afforded
by
computational
chemistry
cannot
be
understated.
activation
strain
model
one
most
powerful
tools
our
arsenal
to
obtain
unparalleled
into
reactivity.
relative
energy
interacting
reactants
evaluated
along
profile
related
rigidity
reactants'
molecular
structure
strength
stabilizing
interactions
between
deformed
reactants:
ΔE(ζ)
=
ΔEstrain(ζ)
+
ΔEint(ζ).
Owing
connectedness
Kohn-Sham
orbital
theory,
able
causal
relationship
both
sterics
electronics
their
mutual
Only
when
accomplished
can
eclipse
phenomenological
explanations
that
commonplace
literature
textbooks
begin
rationally
tune
optimize
transformations.
We
showcase
ideal
tool
elucidate
fundamental
organic
reactions,
small
molecules
metallylenes,
cycloaddition
reactivity
cyclic
diene-
dipolarophiles.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(7), P. 4569 - 4579
Published: Feb. 17, 2022
Dibenziodolium
and
diphenyliodonium
triflates
display
high
catalytic
activity
for
the
multicomponent
reaction
that
leads
to
a
series
of
imidazopyridines.
Density
functional
theory
(DFT)
calculations
indicate
both
salts
can
play
role
hybrid
hydrogen-
halogen-bond-donating
organocatalysts,
which
electrophilically
activate
carbonyl
imine
groups
during
process.
The
ortho-H
atoms
in
vicinal
position
I
atom
dual
role:
forming
additional
noncovalent
bonds
with
ligated
substrate
increasing
maximum
electrostatic
potential
on
σ-hole
at
iodine
owing
effects
polarization.
triflate
exhibits
higher
activity,
results
obtained
from
1H
nuclear
magnetic
resonance
(NMR)
titrations,
conjunction
those
DFT
calculations,
this
could
be
explained
terms
energy
required
rotation
phenyl
ring
cation
ligation
substrate.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(15), P. 10199 - 10207
Published: July 20, 2022
Sulfonium
and
selenonium
salts,
represented
by
S-aryl
dibenzothiophenium
Se-aryl
dibenzoselenophenium
triflates,
were
found
to
exhibit
remarkable
catalytic
activity
in
the
model
Groebke–Blackburn–Bienaymé
reaction.
Kinetic
analysis
density
functional
theory
(DFT)
calculations
indicated
that
their
effect
is
induced
ligation
of
reaction
substrates
σ-holes
on
S
or
Se
atom
cations.
The
experimental
data
although
10-fold
excess
chloride
totally
inhibits
sulfonium
salt
remains
catalytically
active,
which
can
be
explained
experimentally
lower
binding
constant
derivative
comparison
with
analogue.
Both
types
salts
than
dibenziodolium
species.
The Journal of Physical Chemistry A,
Journal Year:
2024,
Volume and Issue:
128(3), P. 507 - 527
Published: Jan. 12, 2024
As
important
noncovalent
interactions,
halogen
bonds
have
been
widely
used
in
material
science,
supramolecular
chemistry,
medicinal
organocatalysis,
and
other
fields.
In
the
past
15
years,
bond
catalysis
has
become
a
developed
field
organocatalysis
for
catalysts'
advantages
of
being
environmentally
friendly,
inexpensive,
recyclable.
Halogen
can
induce
various
organic
reactions,
powerful
alternative
to
fully
explored
hydrogen
catalysis.
From
physical
chemistry
view,
this
perspective
provides
an
overview
latest
progress
key
examples
via
activation
lone
pair
systems
functional
group,
π
systems,
metal
complexes.
The
research
progresses
by
our
group
were
also
introduced.
Physical Chemistry Chemical Physics,
Journal Year:
2021,
Volume and Issue:
23(36), P. 19948 - 19963
Published: Jan. 1, 2021
Hole
interactions
are
known
by
different
names
depending
on
their
key
atom
(
e.g.
halogen,
chalcogen,
triel
or
hydrogen
bonds),
and
the
geometry
of
interaction
(σ,
π,
δ).
Maybe
we
can
make
some
order
analysing
molecular
orbitals?
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(32), P. 4931 - 4940
Published: Jan. 1, 2022
This
Feature
article
presents
recent
representative
applications
of
the
combination
Activation
Strain
Model
reactivity
and
Energy
Decomposition
Analysis
methods
to
understand
Frustrated
Lewis
Pairs
(FLPs).
