Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2891 - 2920
Опубликована: Ноя. 13, 2024
Diaryliodonium
salts
have
become
widely
recognized
as
arylating
agents
in
the
last
two
decades.
Both,
symmetrical
and
unsymmetrical
forms
of
these
serve
effective
electrophilic
reagents
various
organic
syntheses.
The
use
diaryliodoniums
C–C
carbon–heteroatom
bond
formations,
particularly
under
metal-free
conditions,
has
further
enhanced
popularity
reagents.
In
this
review,
we
concentrate
on
arylation
reactions
involving
carbon
other
heteroatoms,
encompassing
rearrangement
absence
any
metal
catalyst,
summarize
advancements
made
five
years.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
Chiral
sulfilimines,
aza
analogues
of
sulfoxides,
are
essential
in
natural
products
and
pharmaceuticals,
highlighting
the
importance
their
synthesis
asymmetric
catalysis.
However,
efficient
approaches
for
synthesizing
chiral
diaryl
sulfilimines
still
rare
challenging,
particularly
those
with
two
sterically
similar
aryl
groups.
Herein,
we
present
a
mild
protocol
generating
diverse
enantioenriched
alkyl
via
copper-catalyzed
enantioselective
S-arylation
N-acyl
sulfenamides
diaryliodonium
salts.
A
bulky
PyBox
ligand
is
crucial
stereocontrol,
delivering
various
up
to
95%
ee
(51
examples).
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 9, 2025
In
this
work,
we
report
an
electrochemical
method
for
the
straightforward
preparation
of
scarcely
accessible
sulfinimidate
esters
from
readily
available
sulfonamides,
thiophenols,
and
alcohols.
Mechanistic
experiments
show
that
sulfur
oxidation
at
anodic
surface
generates
electrophilic
intermediate,
which
subsequently
undergoes
nucleophilic
substitution.
Moreover,
sulfilimines
can
be
obtained
in
moderate-to-excellent
yields
when
thioethers
are
used
as
S-donor
instead
thiophenols
via
a
dehydrogenateive
imination
process.
This
is
also
characterized
by
mild
reaction
condition,
operational
simplicity,
high
atomic
economic
efficiency,
easy
later
drug
synthesis,
modification,
well
scaling
up
to
gram
scale.
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2891 - 2920
Опубликована: Ноя. 13, 2024
Diaryliodonium
salts
have
become
widely
recognized
as
arylating
agents
in
the
last
two
decades.
Both,
symmetrical
and
unsymmetrical
forms
of
these
serve
effective
electrophilic
reagents
various
organic
syntheses.
The
use
diaryliodoniums
C–C
carbon–heteroatom
bond
formations,
particularly
under
metal-free
conditions,
has
further
enhanced
popularity
reagents.
In
this
review,
we
concentrate
on
arylation
reactions
involving
carbon
other
heteroatoms,
encompassing
rearrangement
absence
any
metal
catalyst,
summarize
advancements
made
five
years.
