Skeletal Editing through Cycloaddition and Subsequent Cycloreversion Reactions
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 28, 2025
ConspectusSkeletal
editing,
which
involves
adding,
deleting,
or
substituting
single
multiple
atoms
within
ring
systems,
has
emerged
as
a
transformative
approach
in
modern
synthetic
chemistry.
This
innovative
strategy
addresses
the
ever-present
demand
for
developing
new
drugs
and
advanced
materials
by
enabling
precise
modifications
of
molecular
frameworks
without
disrupting
essential
functional
complexities.
Ideally
performed
at
late
stages
synthesis,
skeletal
editing
minimizes
need
cost-
labor-intensive
processes
often
associated
with
de
novo
thus
accelerating
discovery
optimization
complex
architectures.
While
current
efforts
predominantly
focus
on
monatomic-scale
modifications,
molecules
through
cycloaddition
followed
cycloreversion
offers
unique
to
manipulate
double-atomic
scale.
introduces
possibilities
chemical
transformations
enables
such
double-atom
transmutation,
formal
single-atom
atom
insertion.
Early
examples
relied
inherent
high
reactivity
substrates,
needed
be
sufficiently
active
undergo
possess
good
leaving
groups
subsequent
fragmentation
(cycloreversion)
step.
Recently,
however,
structural
relatively
inert
substrates
become
achievable
substrate
activation
strategies
designed
enhance
either
step.Along
these
lines,
we
recently
developed
dearomative
process
activating
pyridines.
In
simple
high-yielding
operation,
oxazinopyridines
are
readily
obtained
activated
dearomatized
isolable
intermediates.
method
enabled
us
achieve
transformation
pyridines
into
benzenes
naphthalenes
cycloaddition/cycloreversion
sequence.
this
Account,
related
recent
contributions
from
other
research
highlighted
well,
alongside
early
involving
tetrazines,
triazines,
diazines,
similar
heterocycles
reaction
partners.
By
offering
streamlined
route
modify
structures,
approaches
have
demonstrated
their
ability
interconvert
arenes
heteroarenes
shown
significant
potential
late-stage
applications
well
advancing
drug
synthesis
bioactive
molecules.In
future,
will
undoubtedly
see
broader
development
field
editing.
New
should
devised
enable
not
only
incorporation
nitrogen
heteroatoms
rings─rather
than
deletion─but
also
contraction
expand
application
non-aromatic
rings.
We
hope
that
advancements
summarized
Account
inspire
chemists
explore
methodologies.
pushing
boundaries
approaches,
researchers
can
unlock
opportunities
constructing
modifying
frameworks,
eventually
paving
way
chemistry,
biology,
science.
Язык: Английский
Medicinal chemistry-based perspective on thiophene and its derivatives: Exploring the structural insights to discover plausible druggable leads
RSC Medicinal Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Thiophene
is
a
privileged
pharmacophore
in
medicinal
chemistry
owing
to
its
diversified
biological
attributes.
Язык: Английский
First synthesis of (difluoroiodomethyl)thiophenes through double iodation of 2-(difluoromethylene)but-3-yn-1-yl benzyl sulfides
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Double
iodation
of
enyne
sulfides
in
a
mixed
solvent
(CHCl
3
/EtOH
=
50/1)
provided
promising
4-(difluoroiodomethyl)-3-iodo-2-substituted
thiophenes
good
to
excellent
yields.
Язык: Английский
Divergent Access to Furans and Thiophenes by Chalcogenation of 2,3‐Dihydrofurans with Elemental Chalcogens
ChemistrySelect,
Год журнала:
2025,
Номер
10(16)
Опубликована: Апрель 1, 2025
Abstract
A
switchable
chalcogenation
of
2,3‐dihydrofurans
with
elemental
sulfur
or
molecular
oxygen
to
construct
fully
substituted
thiophenes
furans
was
developed.
In
this
version
thiophene
generation,
the
sulfuration
occurs
through
a
cascade
sulfurative
ring
editing
inexpensive
powder.
Conversely,
production
is
enabled
by
aerobic
oxidation
in
basic
media.
Язык: Английский
Electrochemical oxidative C H sulfonylation of thiophenes: Site-selective access to 2-arylsulfonylthiophenes
Tetrahedron Letters,
Год журнала:
2024,
Номер
147, С. 155208 - 155208
Опубликована: Июль 22, 2024
Язык: Английский
Transition‐Metal‐Free Annulation of Sulfonyl‐Derived 1,3‐Enynes: Simple and Efficient Construction of 2,4‐Disubstituted Thiophenes and Vinyl Sulfone‐Tethered 1,2,3‐NH‐Triazoles
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(8)
Опубликована: Май 17, 2024
Abstract
Thiophenes
and
1,2,3‐
NH
‐triazoles
are
important
frameworks
in
pharmaceuticals
advanced
functional
materials.
Vinyl
sulfones
also
blueprint
motifs
medicinal
chemistry,
but
hybrid
analogues
of
‐triazole‐derived
from
vinyl
still
need
to
be
explored.
In
this
report,
we
present
an
efficient
transition‐metal‐free
[4+1]‐thioannulation
sulfonyl‐tethered
1,3‐enynes
with
Na
2
S
the
presence
Cs
CO
3
generate
2,4‐disubstituted
thiophenes
good
high
yields.
We
established
a
formal
[3+2]‐cycloaddition
1,3‐sulfonylenynes
NaN
under
metal‐
base‐free
conditions
synthesize
sulfone‐containing
‐triazole
derivatives
moderate
The
scope
these
protocols
was
successfully
showcased
various
types
bearing
sensitive
groups
complex
structural
scaffolds.
desired
products
were
readily
obtained
group
tolerance
compatibility.
Based
on
existing
results
control
experiments,
plausible
mechanistic
pathways
presented.
Язык: Английский
Electrochemical Oxidative C–H Sulfonylation of Thiophenes: Site-Selective Access to 2-Arylsulfonylthiophenes
Опубликована: Янв. 1, 2024
Язык: Английский
LiBr-Promoted Reaction of β-Ketodithioesters and Thioamides with Sulfoxonium Ylides to Synthesize Functionalized Thiophenes
Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9401 - 9406
Опубликована: Окт. 22, 2024
An
operationally
simple
and
highly
efficient
synthesis
of
functionalized
thiophenes
has
been
developed
by
LiBr
promoted
heteroannulation
β-ketodithioesters
thioamides
with
bench-stable
sulfoxonium
ylides
in
open
air
for
the
first
time.
This
one-pot
strategy
involves
formal
Csp3–H
bond
insertion/intramolecular
cyclization
cascade,
featuring
readily
accessible
starting
materials,
TM
additive-free
condition,
broad
substrate
scope,
high
functional
group
compatibility,
scalability.
Moreover,
carbonyl,
thiomethyl,
amino
groups
resulting
thiophene
provide
a
good
handle
on
downstream
transformations.
Язык: Английский