The Carbene Chemistry of N-Sulfonyl Hydrazones: The Past, Present, and Future
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 10, 2025
N-Sulfonyl
hydrazones
have
been
extensively
used
as
operationally
safe
carbene
precursors
in
modern
organic
synthesis
due
to
their
ready
availability,
facile
functionalization,
and
environmental
benignity.
Over
the
past
two
decades,
there
has
tremendous
progress
chemistry
of
N-sulfonyl
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Many
transfer
reactions
are
unique
cannot
be
achieved
by
any
alternative
methods.
The
discovery
novel
development
highly
enantioselective
new
skeletal
editing
represent
notable
recent
achievements
hydrazones.
This
review
describes
overall
made
hydrazones,
organized
based
on
reaction
types,
spotlighting
current
state-of-the-art
remaining
challenges
addressed
future.
Special
emphasis
is
devoted
identifying,
describing,
comparing
scope
limitations
methodologies,
key
mechanistic
scenarios,
potential
applications
complex
molecules.
Язык: Английский
Triftosylhydrazone in Single-Atom Skeletal Editing
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 16, 2024
ConspectusIn
the
past
decade,
single-atom
skeletal
editing,
which
involves
precise
insertion,
deletion,
or
exchange
of
single
atoms
in
core
skeleton
a
molecule,
has
emerged
as
promising
synthetic
strategy
for
rapid
construction
diversification
complex
molecules
without
laborious
de
novo
processes.
Among
them,
carbene-initiated
editing
is
particularly
appealing
due
to
ready
availability
and
diverse
reactivities
carbene
species.
The
initial
endeavors
modify
heteroarenes
through
carbon-atom
insertion
could
date
back
1881,
when
Ciamician
Denstedt
described
conversion
pyrroles
pyridines
by
trapping
haloform-derived
free
carbene.
Despite
its
potential
value,
general
applicability
this
one-carbon
seen
limited
progress
poor
yields
harsh
reaction
conditions.
Significant
advances
via
were
achieved
only
3
years
Levin,
Ball,
Xu,
Song,
Glorius,
others.
hallmark
these
approaches
facile
halocyclopropanation
followed
regioselective
ring
opening
facilitated
expulsion
halide
ion.
Consequently,
specially
designed
α-halocarbene
precursors,
such
haloform
derivatives,
α-halodiazoacetates,
chlorodiazirines,
α-chlorodiazo
oxime
esters,
can
be
employed
achieve
Ciamician–Denstedt-type
editing.
This
not
limits
types
functional
groups
installed
on
expansion
products
but
also
prevents
their
widespread
adoption,
especially
late-stage
contexts.
enduring
quest
develop
environmentally
friendly
versatile
superior
group
compatibility,
application
diversifications
investigation
mechanistic
insights
into
carbon
reactions
remain
fundamental
objective.In
our
over
5
years,
we
have
developed
o-trifluoromethylbenzenesulfonylhydrazones
(named
Triftosylhydrazones)
operationally
safe
easily
decomposable
diazo
surrogates
explored
various
challenging
catalytic
transfer
reactions.
Recently,
put
great
efforts
expanding
scope
unlocking
triftosylhydrazones
precursors
Since
2018,
realized
range
acyclic
1,3-dicarbonyls
with
silver
carbenes
access
1,4-dicarbonyls,
proceeding
cyclopropanation/ring-opening
process.
Inspired
results,
recently
demonstrated
series
transition-metal-catalyzed
highly
selective
medicinally
interesting
like
pyrroles,
indoles,
1,2-diazoles
carbenic
insertion.
We
then
strained
three-membered
nitrogen-
oxygen-containing
heterocycles
single-carbon
atoms.
In
Account,
present
an
overview
achievements
heterocycles,
organized
based
three
situ-generated
key
intermediates,
cyclopropane,
N-ylide,
O-ylide
from
focus
scopes,
features,
applications.
hope
that
Account
will
provide
valuable
contribute
development
new
methodologies
both
chemistry
fields.
Язык: Английский
Advances in the Synthesis of Cyclopropylamines
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 6, 2025
Cyclopropylamines
are
an
important
subclass
of
substituted
cyclopropanes
that
combine
the
unique
electronic
and
steric
properties
with
presence
a
donor
nitrogen
atom.
In
addition
to
their
in
diverse
array
biologically
active
compounds,
cyclopropylamines
utilized
as
synthetic
intermediates,
particularly
ring-opening
or
cycloaddition
reactions.
Consequently,
synthesis
these
compounds
has
constituted
significant
research
topic,
evidenced
by
abundant
published
methods.
widely
used
Curtius
rearrangement,
classical
cyclopropanation
methods
have
been
adapted
integrate
function
(Simmons-Smith
reaction,
metal-catalyzed
reaction
diazo
on
olefins,
Michael-initiated
ring-closure
reactions)
advances
enantioselective
synthesis.
More
recently,
specific
developed
for
preparation
aminocyclopropane
moiety
(Kulinkovich
reactions
applied
amides
nitriles,
cyclopropenes,
involving
C-H
functionalization,
...).
The
topic
this
review
is
present
different
cyclopropylamine
derivatives,
aim
covering
methodological
best
possible,
highlighting
scope,
stereochemical
aspects
future
trends.
Язык: Английский
Copper-Catalyzed Cross-Coupling of Bicyclobutanes with Triftosylhydrazone Leading to Skipped Dienes
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 4, 2025
Here,
we
report
a
protocol
for
the
synthesis
of
skipped
dienes
through
cross-coupling
bicyclo[1.1.0]butanes
with
trifluoromethyl
triftosylhydrazones.
The
reaction
is
run
using
TpBr3Cu(NCMe)
as
catalyst
to
give
access
library
trifluoromethylated
(32
examples,
≤98%
yield)
excellent
E/Z
selectivity
under
mild
and
operationally
safe
conditions.
presented
methods
proved
be
compatible
various
functionalized
Язык: Английский
Silver-Catalyzed Doyle–Kirmse Reaction of Allyl Sulfides with Vinyl Triftosylhydrazones
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Here,
we
report
a
general
and
practical
Doyle-Kirmse
reaction
of
allyl/propargyl
sulfides
with
donor-only
vinyl
carbenes
generated
in
situ
from
triftosylhydrazones
the
presence
silver
catalyst.
This
protocol
features
mild
conditions,
exhibits
broad
substrate
scope
exceptional
functional
group
tolerance,
provides
corresponding
1,5-dienyl
1,4-enallenyl
high
yields.
Moreover,
gram-scale
synthesis,
late-stage
modifications
complex
molecules,
post-synthetic
transformations
were
performed
to
demonstrate
applicability
this
protocol.
Язык: Английский
Rational construction of “all-in-one” vertically aligned copper single-atomic graphene oxide based evaporators for integrated solar steam generation and sulfate radical-advanced oxidation process
Separation and Purification Technology,
Год журнала:
2025,
Номер
unknown, С. 132960 - 132960
Опубликована: Апрель 1, 2025
Язык: Английский