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
Doyle–Kirmse Reaction on Alkynyl Hydrazone Carboxylates: Synthesis of 1,4-Allenyne and 1,5-Enyne Thioaryl Carboxylates
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2135 - 2140
Опубликована: Март 1, 2024
The
first
Doyle-Kirmse
reaction
on
alkynyl
diazoacetates
using
allyl/propargyl
sulfides
is
reported.
development
provides
diversified
1,5-enyne
and
1,4-allenyne
thioaryl
carboxylates
in
good
yields
under
ligand-/additive-free
AuCl
Rh
Язык: Английский
Decomposition of Alkynyl Hydrazones: Synthesis of Allenoates, Dihaloallenoates, and Angularly Fused Tricyclic Azepines
Organic Letters,
Год журнала:
2023,
Номер
25(36), С. 6607 - 6612
Опубликована: Сен. 5, 2023
An
unprecedented
decomposition
of
unprotected
alkynyl
hydrazones
is
attempted
that
has
provided
allenoates,
tetrasubstituted
α,γ-dihaloallenoates,
and
functionalized
tricyclic
azepines.
A
reaction
with
N-halosuccinimides
captures
the
electrophile
in
2-fold
delivers
fully
substituted
dibromo-
diiodoallenoates
good
yields.
In
addition,
a
DABCO-promoted
Wolff-Kishner
reduction
hydrazones,
followed
by
isomerization,
provides
versatile
allenoates
under
mild
conditions.
contrast,
similar
ambiphilic
DBU
furnishes
completely
different
azepine
scaffold
excellent
yield
diastereoselectivity.
Язык: Английский
Synthesis of Tetrasubstituted 1,4-Dicarbonyl (Z)-2,3-Dihaloalkenes via Electrophilic Halogenation of Alkynyl Hydrazones
Organic Letters,
Год журнала:
2023,
Номер
25(39), С. 7236 - 7241
Опубликована: Сен. 25, 2023
A
highly
practical
and
stereoselective
route
to
1,4-dicarbonyl
2,3-dihaloalkenes
is
presented.
The
strategy
involves
bench-stable
unprotected
alkynyl
hydrazones
commercially
available
N-halosuccinimides
that
provide
γ-oxo-α,β-(Z)-dihaloenoates
in
excellent
yields
with
complete
Z-selectivity.
protocol
also
furnishes
vicinal
dihaloalkenes
two
different
halogen
atoms.
Also,
a
straightforward
one-pot
synthesis
of
dihaloenoates
from
readily
accessible
2-oxo-3-butynoate
demonstrated.
In
addition,
potential
synthetic
transformations
4-oxo-2,3-dibromoenoates
are
explored,
which
include
the
valuable
five-
six-membered
heterocycles.
Язык: Английский
(E)-1-(1-(Benzofuran-2-yl)ethylidene)-2-(2,4,6-trichlorophenyl)hydrazine
Molbank,
Год журнала:
2024,
Номер
2024(1), С. M1790 - M1790
Опубликована: Март 11, 2024
The
reaction
of
a
mixture
equimolar
quantities
2-acetylbenzofuran
and
(2,4,6-trichlorophenyl)hydrazine
in
ethanol
containing
concentrated
hydrochloric
acid
(0.2
mL;
37%)
as
catalyst
under
reflux
for
two
hours
yielded
1-(1-(benzofuran-2-yl)ethylidene)-2-(2,4,6-trichlorophenyl)hydrazine.
crude
product
was
purified
by
crystallization
using
dimethylformamide
to
provide
the
title
heterocycle
90%
yield.
structure
new
confirmed
through
X-ray
diffraction
spectral
analyses.
Язык: Английский
(E)-1-(4-Methoxyphenyl)-5-methyl-4-(1-phenyl-4-((2-(2,4,6-trichlorophenyl)hydrazineylidene)methyl)-1H-pyrazol-3-yl)-1H-1,2,3-triazole
Molbank,
Год журнала:
2024,
Номер
2024(2), С. M1798 - M1798
Опубликована: Март 28, 2024
The
reaction
of
equimolar
quantities
3-(1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-triazol-4-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde
and
(2,4,6-trichlorophenyl)hydrazine
in
ethanol
containing
concentrated
hydrochloric
acid
(0.2
mL;
37%)
as
a
catalyst
under
reflux
for
2
h
yielded
1-(1-(benzofuran-2-yl)ethylidene)-2-(2,4,6-trichlorophenyl)hydrazine.
crude
produced
was
purified
by
crystallization
using
dimethylformamide
to
provide
the
title
heterocycle
95%
yield.
structure
newly
synthesized
confirmed
through
X-ray
diffraction
spectral
analyses.
Язык: Английский
Rhodium(II)-Catalyzed Alkynyl Carbene Insertion into N–H Bonds
Organic Letters,
Год журнала:
2024,
Номер
26(23), С. 4887 - 4892
Опубликована: Июнь 6, 2024
The
first
insertion
of
an
alkynyl
carbene
into
N–H
bonds
under
Rh-catalysis
is
developed.
Alkynyl
hydrazone
carboxylates
are
used
as
donor–acceptor
precursors
and
exquisitely
inserted
the
various
amines,
amides,
1,2-diamines.
A
wide
variety
3-alkynyl
3,4-dihydroquinoxalin-2(1H)-ones
densely
functionalized
α-alkynyl
α-amino
esters
obtained
in
good
to
excellent
yields.
Further,
chemoselective
reactions,
mechanistic
studies,
synthetic
transformations
for
obtaining
valuable
heterocycles
demonstrated.
Язык: Английский