Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 27, 2025
Considerable
progress
has
been
made
over
decades
in
synthetic
organic
chemistry
order
to
build
up
molecular
complexity,
often
through
the
design
of
advanced
catalytic
systems.
Yet,
simply
exposing
molecules
benchmark
oxidants
catalyst
free
conditions
can
sometimes
lead
surprising
and
highly
valuable
products.
Thus,
a
method
for
accessing
rare
9-membered
ketolactams
is
herein
described,
under
mild
oxidative
conditions.
Key
18O
17O
label
experiments
revealed
an
unexpected
oxygen
atom
migration
event
ring
expansion
process.
The
scope,
mechanism,
applications,
9
7
membered
contraction
opportunities
are
discussed.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 13, 2024
Hypervalent
iodine(III)
compounds
have
found
wide
application
in
modern
organic
chemistry
as
environmentally
friendly
reagents
and
catalysts.
iodine
are
commonly
used
synthetically
important
halogenations,
oxidations,
aminations,
heterocyclizations,
various
oxidative
functionalizations
of
substrates.
Iodonium
salts
arylating
reagents,
while
iodonium
ylides
imides
excellent
carbene
nitrene
precursors.
Various
derivatives
benziodoxoles,
such
azidobenziodoxoles,
trifluoromethylbenziodoxoles,
alkynylbenziodoxoles,
alkenylbenziodoxoles
group
transfer
the
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Development
hypervalent
catalytic
systems
discovery
highly
enantioselective
reactions
chiral
represent
a
particularly
recent
achievement
field
chemistry.
Chemical
transformations
promoted
by
many
cases
unique
cannot
be
performed
any
other
common,
non-iodine-based
reagent.
This
review
covers
literature
published
mainly
last
7-8
years,
between
2016
2024.
Royal Society Open Science,
Journal Year:
2022,
Volume and Issue:
9(1)
Published: Jan. 1, 2022
The
bioconjugation
of
proteins-that
is,
the
creation
a
covalent
link
between
protein
and
any
other
molecule-has
been
studied
for
decades,
partly
because
numerous
applications
conjugates,
but
also
due
to
technical
challenge
it
represents.
Indeed,
proteins
possess
inner
physico-chemical
properties-they
are
sensitive
polynucleophilic
macromolecules-that
make
them
complex
substrates
in
conjugation
reactions.
This
complexity
arises
from
mild
conditions
imposed
by
their
sensitivity
selectivity
issues,
viz
precise
control
site
on
protein.
After
decades
research,
strategies
reagents
have
developed
address
two
aspects
this
selectivity:
chemoselectivity-harnessing
reacting
chemical
functionality-and
site-selectivity-controlling
amino
acid
residue-most
notably
thanks
participation
synthetic
chemistry
effort.
review
offers
an
overview
these
strategies,
insisting
those
employing
native
as
substrates,
shows
that
field
is
active
exciting,
especially
chemists
seeking
new
challenges.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(12), P. 1589 - 1604
Published: Jan. 1, 2023
Although
alkynes
are
one
of
the
smallest
functional
groups,
they
among
most
versatile
building
blocks
for
organic
chemistry,
with
applications
ranging
from
biochemistry
to
material
sciences.
Alkynylation
reactions
have
traditionally
relied
on
use
acetylenes
as
nucleophiles.
The
discovery
and
development
ethynyl
hypervalent
iodine
reagents
allowed
greatly
expand
transfer
electrophilic
synthons.
In
this
feature
article
progress
in
field
since
2018
will
be
presented.
After
a
short
introduction
alkynylation
reagents,
developments
synthesis
alkynyl
discussed.
Their
recent
base-mediated
transition-metal
catalyzed
alkynylations
described.
Progress
radical-based
atom-economical
transformations
then
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(16), P. 2653 - 2675
Published: April 21, 2023
Abstract
Hypervalent
iodine
compounds
have
found
broad
application
in
modern
organic
chemistry
as
reagents
and
catalysts.
Cyclic
hypervalent
based
on
the
benziodoxole
heterocyclic
system
higher
stability
compared
to
their
acyclic
analogues,
which
makes
possible
preparation
safe
handling
of
with
special
ligands
such
azido,
cyano,
trifluoromethyl
groups.
Numerous
iodine‐substituted
derivatives
been
prepared
utilized
for
transfer
substituent
substrate.
Reactions
these
substrates
can
be
performed
under
metal‐free
conditions,
presence
transition
metal
catalysts,
or
using
photocatalysts
photoirradiation
conditions.
In
this
review,
we
focus
most
recent
synthetic
applications
cyclic
iodine(III)
following
ligands:
N
3
,
NHR,
CN,
CF
SCF
OR,
OAc,
ONO
2
C(=N
)CO
R.
The
review
covers
literature
published
mainly
last
5
years.
Acta Pharmaceutica Sinica B,
Journal Year:
2023,
Volume and Issue:
14(3), P. 1030 - 1076
Published: Nov. 18, 2023
Synthetic
chemistry
plays
an
indispensable
role
in
drug
discovery,
contributing
to
hit
compounds
identification,
lead
optimization,
candidate
drugs
preparation,
and
so
on.
As
Nobel
Prize
laureate
James
Black
emphasized,
"the
most
fruitful
basis
for
the
discovery
of
a
new
is
start
with
old
drug"
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 2, 2025
ConspectusDuring
the
past
few
years,
interest
among
organic
synthesis
practitioners
in
use
of
sulfonium
salts
has
exponentially
growth.
This
can
arguably
be
attributed
to
a
series
specific
factors:
(a)
The
recent
development
more
direct
and
efficient
protocols
for
these
species,
which
make
reagents
wide
structural
variety
easily
available
multigram
scale.
(b)
recognition
that
reactivity
resembles
hypervalent
iodine
compounds,
therefore,
they
used
as
effective
replacement
such
species
most
their
applications.
(c)
Their
intrinsic
thermal
stability
tolerance
air
moisture,
clearly
surpass
I(III)-reagents
analogue
reactivity,
facilitate
purification,
isolation
well-defined
storage,
safely
handling
on
larger
(d)
Finally,
possibility
further
functionalize
once
sulfur-containing
platform
been
incorporated.
Specifically,
this
last
synthetic
approach
is
not
trivial
when
working
with
I(III)-species
facilitates
access
no
counterpart
I(III)
realm.This
renewed
led
improvement
already
existing
transformations
well
discovery
unprecedented
ones;
particular,
by
incorporate
partners
traditional
cross-coupling
C–H
activation
steps
or
combine
them
modern
technologies
photocatalysis
electrosynthesis.
In
Account,
originally
prepared
our
laboratory
will
outlined
compared
I(III)-counterparts.
Some
are
now
commercially
available,
started
spread
widely
across
chemistry
community,
helping
speed
process
identification
potentially
bioactive
products
new
functionaliced
materials.
However,
challenges
still
remain.
characterized
an
optimal
balance
between
site-selectivity,
showing
broader
compatibility
toward
sensitive
functional
groups
need.
addition,
often
makes
necessary
(sophisticated)
catalysts
activate
latent
hidden
structures.
Although
priori
one
see
fact
disadvantage,
it
might
actually
decisive
harvest
full
potential
because
surely
preparation
operational
context
I(III)-chemistry.
If
becomes
true,
may
contribute
expediting
retrosynthetic
disconnections
that,
date,
impossible.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(7)
Published: Oct. 21, 2021
Hypervalent
iodine
compounds
are
powerful
reagents
for
the
development
of
novel
transformations.
As
they
exhibit
low
toxicity,
high
functional
group
tolerance,
and
stability
in
biocompatible
media,
have
been
used
functionalization
biomolecules.
Herein,
we
report
recent
advances
up
to
June
2021
peptide
protein
modification
using
hypervalent
reagents.
Their
use
as
transfer
or
oxidizing
is
discussed
this
Minireview,
including
methods
targeting
polar,
aromatic,
aliphatic
amino
acids
termini.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(66)
Published: Aug. 16, 2022
Cysteine
bioconjugation
serves
as
a
powerful
tool
in
biological
research
and
has
been
widely
used
for
chemical
modification
of
proteins,
constructing
antibody-drug
conjugates,
enabling
cell
imaging
studies.
conjugation
reactions
with
fast
kinetics
exquisite
selectivity
have
under
heavy
pursuit
they
would
allow
clean
protein
just
stoichiometric
amounts
reagents,
which
minimizes
side
reactions,
simplifies
purification
broadens
functional
group
tolerance.
In
this
concept,
we
summarize
the
recent
advances
cysteine
bioconjugation,
discuss
mechanism
principles
that
underlie
high
efficiencies
newly
developed
reactive
reagents.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(1), P. 380 - 449
Published: Dec. 14, 2023
Proteins
are
multifunctional
large
organic
compounds
that
constitute
an
essential
component
of
a
living
system.
Hence,
control
over
their
bioconjugation
impacts
science
at
the
chemistry-biology-medicine
interface.
A
chemical
toolbox
for
precision
engineering
can
boost
healthcare
and
open
gateway
directed
or
therapeutics.
Such
remained
elusive
long
time
due
to
complexity
presented
by
pool
functional
groups.
The
precise
single-site
modification
protein
requires
method
address
combination
selectivity
attributes.
This
review
focuses
on
guiding
principles
segregate
them
simplify
task
method.
disintegration
systematically
employs
multi-step
transformation
deconvolute
challenges.
It
constitutes
disintegrate
(DIN)
theory
offers
additional
parameters
tuning
in
bioconjugation.
outlines
hurdles
faced
methods.
elaborates
developments
perspective
DIN
demonstrate
simultaneous
regulation
reactivity,
chemoselectivity,
site-selectivity,
modularity,
residue
specificity,
specificity.
discusses
progress
such
methods
construct
antibody
conjugates
biologics,
including
antibody-fluorophore
antibody-drug
(AFCs
ADCs).
also
briefs
how
this
knowledge
assist
developing
small
molecule-based
covalent
inhibitors.
In
process,
it
highlights
opportunity
hypothesis-driven
routes
accelerate
discoveries
selective
establish
new
targetome
proteins
antibodies.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(12)
Published: Jan. 24, 2023
A
simple
process
for
the
oxy-monofluoromethylation
of
alkenes
is
described.
In
combination
with
visible-light
copper(I)
photoredox
catalysis,
an
easily
accessible
iodine(III)
reagent
containing
monofluoroacetoxy
ligands
serves
as
a
powerful
source
monofluoromethyl
(CH2
F)
radical,
enabling
step
economical
synthesis
γ-fluoro-acetates
from
broad
range
olefinic
substrates
under
mild
conditions.
Applications
to
late-stage
diversification
derived
complex
molecules,
amino
acids
and
fluoromethylated
heterocycles
are
also
demonstrated.