Angewandte Chemie,
Год журнала:
2022,
Номер
134(39)
Опубликована: Июль 27, 2022
Abstract
Here
we
report
an
α‐thianthrenium
carbonyl
species,
as
the
equivalent
of
α‐carbonyl
carbocation,
which
is
generated
by
radical
conjugate
addition
a
trifluoromethyl
thianthrenium
salt
to
Michael
acceptors.
The
reactivity
allows
for
synthesis
C
α
‐tetrasubstituted
α‐
and
β‐amino
acid
analogues
via
Ritter
reaction
acetonitrile.
Addition
hydroxide,
methoxide,
even
fluoride
can
afford
α‐heteroatom
substituted
α‐phenylpropanoates.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 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.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(39)
Опубликована: Авг. 9, 2022
Here
we
report
an
α-thianthrenium
carbonyl
species,
as
the
equivalent
of
α-carbonyl
carbocation,
which
is
generated
by
radical
conjugate
addition
a
trifluoromethyl
thianthrenium
salt
to
Michael
acceptors.
The
reactivity
allows
for
synthesis
C
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
present
a
rapid
Au(
i
)-catalyzed
strategy
for
N
-heteroarene
functionalization
using
TBAF
as
nucleophile
or
base.
The
method
provides
excellent
yields,
broad
substrate
scope
and
functional
group
tolerance,
enabling
diverse
transformations.
Chemical Science,
Год журнала:
2021,
Номер
13(4), С. 1169 - 1176
Опубликована: Дек. 27, 2021
Control
over
chemo-
and
regioselectivity
is
a
critical
issue
in
the
heterobiaryl
synthesis
via
C–H
oxidative
coupling.
To
address
this
challenge,
strategy
to
invert
normal
polarity
of
indoles
was
developed.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(21), С. 15590 - 15597
Опубликована: Окт. 11, 2024
A
two-step
umpolung
approach
to
the
diastereoselective
synthesis
of
aldols
was
developed,
in
which
a
conjugated
nitroalkene
is
used
as
synthetic
equivalent
enolonium
cation,
while
sulfur
ylide
acts
α-carbinol
anion.
The
resulting
isoxazoline
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(12)
Опубликована: Окт. 6, 2023
Abstract
Amides
are
important
carboxylic
acid
derivatives,
having
wide
applications
in
chemistry,
biochemistry,
and
material
science.
Due
to
the
conjugation
(n
N
‐π*
C=O
),
carbonyl
group
of
amides
is
least
electrophilic
C
alpha
−H
bond
acidic
among
thereby
making
it
challenging
develop
highly
efficient
selective
transformations
based
on
amides.
Reactivity
umpolung
refers
reversion
polarity
a
functional
group.
The
idea
inverting
innate
organic
groups,
initially
introduced
by
Wittig
later
popularized
Seebach,
marks
pivotal
conceptual
breakthrough
synthesis.
In
contrast
progress
for
aldehyde,
has
proved
only
recently
made
notable
progress.
Following
elegant
design,
C1
amide
can
become
nucleophilic,
C2
be
electrophilic.
this
review,
we
attempt
summarize
reported
examples
that
broadly
categorized
as
reactivity
This
review
structured
around
through
radical
or
carbanion
reactions,
well
activation
unique
properties
Weinreb
amide.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Окт. 19, 2023
α-Carbonyl
cations
are
the
umpolung
forms
of
synthetically
fundamental
α-carbonyl
carbanions.
They
highly
reactive
yet
rarely
studied
and
utilized
species
their
precursors
were
rather
limited.
Herein,
we
report
catalyst-controlled
divergent
generations
from
single
alkyne
functionalities
interception
them
via
Wagner-Meerwein
rearrangement.
Two
chemodivergent
catalytic
systems
have
been
established,
leading
to
two
different
types
and,
eventually,
products,
i.e.
α,β-
β,γ-unsaturated
carbonyl
compounds.
Broad
spectrum
alkynes
including
aryl
alkyne,
ynamide,
alkynyl
ether,
sulfide
could
be
migration
priorities
groups
in
rearrangement
step
was
elucidated.
Density
functional
theory
calculations
further
supported
intermediacy
N-O
bond
cleavage
both
systems.
Another
key
feature
this
methodology
fragmentation
inert
tert-butyl
into
readily
transformable
olefin
functionalities.
The
synthetic
potential
highlighted
by
scale-up
reactions
downstream
diversifications
formal
synthesis
nicotlactone
B
galbacin.
