Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents
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.
Language: Английский
Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents
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.
Language: Английский
Organohypervalent heterocycles
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4786 - 4827
Published: Jan. 1, 2024
This
review
summarizes
structural
and
synthetic
aspects
of
heterocyclic
molecules
incorporating
an
atom
a
hypervalent
main-group
element.
The
higher
thermal
stability
heterocycles,
as
compared
to
their
acyclic
analogs,
adds
special
feature
chemistry.
Language: Английский
Amino‐ and Alkoxybenziodoxoles: Facile Preparation and Use as Arynophiles
Kazuya Kanemoto,
No information about this author
Ken Yoshimura,
No information about this author
Koki Ono
No information about this author
et al.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(29)
Published: March 18, 2024
Abstract
We
report
here
on
the
facile
synthesis
of
amino‐
and
alkoxy‐λ
3
‐iodanes
supported
by
a
benziodoxole
(BX)
template
their
use
as
arynophiles.
The
alkoxy‐BX
derivatives
can
be
readily
synthesized
reacting
respective
amines
or
alcohols
with
chlorobenziodoxole
in
presence
suitable
base.
Unlike
previously
known
nitrogen‐
oxygen‐bound
iodane
compounds,
which
have
primarily
been
employed
electrophilic
group
transfer
agents
oxidants,
present
reagents
manifest
themselves
nucleophilic
amino
alkoxy
toward
arynes.
This
reactivity
leads
to
aryne
insertion
into
N−I(III)
O−I(III)
bond
afford
ortho
‐amino‐
‐alkoxy‐arylbenziodoxoles,
compounds
nontrivial
procure
existing
methods.
BX
these
products
exhibits
excellent
leaving
ability,
enabling
diverse
downstream
transformations.
Language: Английский
Visible‐Light‐Induced C−H Amidation of (Hetero)arenes with Hypervalent Iodine(III) Reagents
Asian Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
Abstract
A
visible‐light‐promoted
C−H
amidation
of
(hetero)arenes
with
hypervalent
iodine
reagents
has
been
successfully
achieved
good
yields.
The
high
efficiency,
broad
substrate
range
and
functional
group
compatibility
demonstrated
the
utility
method.
Moreover,
this
protocol
was
suitable
for
late‐stage
functionalization
natural
products.
Mechanistic
studies
have
shown
that
N‐centred
saccharin
radical
mediates
arenes.
Language: Английский
Iodine-Mediated α-C–H Amination of Carbonyl Compounds via Nitrogen-Directed Oxidative Umpolung
Manman Wang,
No information about this author
Xiaofei Yi,
No information about this author
Wenjun Ye
No information about this author
et al.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 8751 - 8760
Published: June 12, 2023
A
new
synthetic
strategy
for
direct
C(sp3)–H
amination
of
carbonyl
compounds
at
their
α-carbon
has
been
established
employing
molecular
iodine
and
nitrogen-directed
oxidative
umpolung.
In
this
transformation,
acts
not
only
as
an
iodinating
reagent
but
also
a
Lewis
acid
catalyst,
both
the
nitrogen-containing
moiety
group
in
substrate
play
important
roles.
This
approach
is
applicable
to
broad
variety
substrates,
including
esters,
ketones,
amides.
Its
features
include
no
requirement
transition
metals,
mild
reaction
conditions,
short
times,
gram-scale
synthesis.
Language: Английский
Photoexcitation of (diarylmethylene)amino benziodoxolones for alkylamination of styrene derivatives with carboxylic acids
Daichi Okumatsu,
No information about this author
Kensuke Kiyokawa,
No information about this author
Linh Tran Bao Nguyen
No information about this author
et al.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
15(3), P. 1068 - 1076
Published: Dec. 12, 2023
The
alkylamination
of
alkenes
using
pristine
carboxylic
acids
was
achieved
by
the
photoexcitation
(diarylmethylene)amino
benziodoxolones
(DABXs),
which
serve
as
both
an
oxidant
and
aminating
reagent
(an
iminyl
radical
precursor).
developed
method
is
a
simple
photochemical
reaction
without
need
for
external
photosensitizers
shows
broad
substrate
scope
aliphatic
leading
to
formation
primary,
secondary,
tertiary
alkyl
radicals,
thus
enabling
facile
synthesis
various
structurally
complex
amines.
Mechanistic
investigations
including
transient
absorption
spectroscopy
measurements
laser
flash
photolysis
(LFP)
disclosed
unique
reactivity
DABXs,
undergoes
homolysis
their
I-N
bonds
give
Language: Английский
Reactivity of hypervalent iodine(III) reagents bearing a benzylamine with sulfenate salts
Beatriz Dedeiras,
No information about this author
Catarina Caldeira,
No information about this author
José Cunha
No information about this author
et al.
Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 3281 - 3289
Published: Dec. 19, 2024
The
reactivity
of
our
recently
disclosed
hypervalent
iodine
reagents
(HIRs)
bearing
a
benzylamine
with
in
situ-generated
sulfenate
salts
was
investigated.
Under
the
studied
conditions
sulfonamides
have
been
obtained
up
to
52%
yield.
This
reaction
has
extended
variety
HIRs
and
explore
different
these
new
reagents.
A
plausible
mechanism
is
proposed,
suggesting
possible
radical
pathway.
Language: Английский