European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(47)
Опубликована: Окт. 10, 2022
Abstract
Aza‐oxyallyl
cations,
as
proposed
by
Sheehan
in
the
1960s
have
garnered
significant
attention
among
synthetic
organic
community,
owing
to
their
diverse
reactivity
profile
for
constructing
N‐scaffolds
of
biological
interest.
During
its
initial
growth,
aza‐oxyallyl
cations
were
used
effectively
a
3‐unit
synthon
1,3
dipoles
create
N‐heterocycles
via
cycloaddition
reactions,
wherein
cation
served
electrophilic
counterpart.
Recently,
new
variations
been
reported,
including
usage
1,4
dipole
domino
and
unique
alkylating
ability
heteroatoms.
This
review
article
provides
an
update
recent
developments
this
area
prevailing
mechanistic
insight.
Polymers,
Год журнала:
2020,
Номер
12(4), С. 881 - 881
Опубликована: Апрель 10, 2020
This
paper
reports
on
synthesis,
acid–base
properties,
and
self-structuring
in
water
of
a
chiral
polyamidoamino
acid,
M-l-Gln,
obtained
from
the
polyaddition
N,N′-methylenebisacrylamide
with
l-glutamine,
potential
establishing
hydrogen
bonds
through
its
prim-amide
pendants.
The
M-l-Gln
showed
pH-responsive
circular
dichroism
spectra,
revealing
ordered
conformations.
Structuring
was
nearly
insensitive
to
ionic
strength
but
sensitive
denaturing
agents.
NMR
diffusion
studies
were
consistent
population
unimolecular
nanoparticles
thus
excluding
aggregation.
had
highest
molecular
weight
hydrodynamic
radius
among
all
acids
described.
Possibly,
transient
between
l-glutamine
molecules
growing
chains
facilitated
reaction.
Theoretical
modeling
that
assumed
pH-dependent
self-ordered
coil
conformations
main
chain
transoid
arrangements
reminiscent
protein
hairpin
motif
owing
intramolecular
dipole
moments
bonds.
latter
most
numerous
at
isoelectric
point
(pH
4.5),
where
they
mainly
involved
even
topologically
distant
amide
N–H
side
C=O
brought
proximity
by
structuring.
Hydrogen
pH
4.5
also
suggested
variable
temperature
NMR.
2D
NOESY
experiments
confirmed
formation
compact
structures
analysis
chain/side
contacts,
line
MD
simulations.
ChemistryOpen,
Год журнала:
2020,
Номер
9(2), С. 100 - 170
Опубликована: Янв. 13, 2020
The
aim
of
this
review
is
to
highlight
the
rich
chemistry
α-haloamides
originally
mainly
used
discover
new
C-N,
C-O
and
C-S
bond
forming
reactions,
later
widely
employed
in
C-C
cross-coupling
reactions
with
C(sp3),
C(sp2)
C(sp)
coupling
partners.
Radical-mediated
transformations
bearing
a
suitable
located
unsaturated
has
proven
be
straightforward
alternative
access
diverse
cyclic
compounds
by
means
either
radical
initiators,
transition
metal
redox
catalysis
or
visible
light
photoredox
catalysis.
On
other
hand,
cycloadditions
α-halohydroxamate-based
azaoxyallyl
cations
have
garnered
significant
attention.
Moreover,
view
important
role
life
materials
science
difluoroalkylated
compounds,
wide
range
catalysts
been
developed
for
efficient
incorporation
difluoroacetamido
moieties
into
activated
as
well
unactivated
substrates.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(30)
Опубликована: Май 27, 2023
Access
to
1,3-functionalized
azetidines
through
a
diversity-oriented
approach
is
highly
sought-after
for
finding
new
applications
in
drug-discovery.
To
this
goal,
strain-release-driven
functionalization
of
azabicyclo[1.1.0]-butane
(ABB)
has
generated
significant
interest.
Through
appropriate
N-activation,
C3-substituted
ABBs
are
shown
render
tandem
N/C3-fucntionalization/rearrangement,
furnishing
azetidines;
although,
modalities
such
N-activation
vis-à-vis
N-functionalization
remain
limited
selected
electrophiles.
This
work
showcases
versatile
cation-driven
activation
strategy
ABBs.
And
capitalizes
on
the
use
Csp3
precursors
amenable
forming
reactive
(aza)oxyallyl
cations
situ.
Herein,
leads
formation
congested
C-N
bond,
and
effective
C3
activation.
The
concept
was
extended
formal
[3+2]
annulations
involving
ABBs,
leading
bridged
bicyclic
azetidines.
Besides
fundamental
appeal
paradigm,
operational
simplicity
remarkable
diversity
should
engender
its
prompt
synthetic
medicinal
chemistry.
Organic Letters,
Год журнала:
2021,
Номер
23(4), С. 1451 - 1456
Опубликована: Фев. 1, 2021
Oxindoles
and
β-lactams
are
attractive
structural
motifs
because
of
their
unique
biological
importance.
However,
the
fusion
two
moieties
featuring
3,3′-spirocyclic
scaffolds
is
a
challenging
task
in
organic
synthesis.
Herein
we
designed
novel
type
oxindole-based
azaoxyallyl
cation
synthons,
which
could
readily
participate
[3
+
1]
cyclization
with
sulfur
ylides.
With
this
protocol,
collection
3,3-spiro[β-lactam]-oxindoles
were
facilely
produced
up
to
94%
yield
perfect
diastereoselectivity.
Chemical Communications,
Год журнала:
2021,
Номер
57(62), С. 7610 - 7624
Опубликована: Янв. 1, 2021
Palladium
has
proven
to
be
effective
in
catalyzing
the
(hetero)annulation
of
C[double
bond,
length
as
m-dash]C
bonds
with
ambiphilic
organo(pseudo)halides.
Through
employment
appropriate
coupling
partners,
efficient
annulation
a
variety
allenes,
1,3-dienes,
strained
alkenes,
styrenes,
and
other
bond
variants
can
achieved
provide
direct
access
numerous
useful
hetero-
carbocyclic
scaffolds.
In
this
Feature
Article,
we
summarize
palladium-catalyzed
methods
reported
since
2005
(spanning
just
over
15
years)
discuss
outstanding
challenges
area
study.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 10, 2022
In
this
study,
we
systematically
evaluate
different
ambiphilic
organohalides
for
their
ability
to
participate
in
anti-selective
carbo-
or
heteroannulation
with
non-conjugated
alkenyl
amides
under
Pd
Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(2), С. 101822 - 101822
Опубликована: Фев. 1, 2024
Catalytic
asymmetric
alkylation
of
α-halogenated
enolates
is
a
challenging
issue
due
to
their
extenuated
nucleophilicity
and
the
electrophilic
oxidative
nature
parent
α-Cl/Br
carbonyl
compounds.
Herein,
by
means
coordination-stabilized
copper(I)
α-F/Cl
as
nucleophiles,
catalytic
2-azaarylesters
achieved
with
broad
substrate
scope
on
alkyl
halides,
which
constructs
halogenated
tetrasubstituted
carbon
centers
in
good
excellent
yields
high
enantioselectivity.
Moreover,
present
protocol
successfully
applied
building
chiral
quaternary
centers.
Finally,
synthetic
utilities
products
are
demonstrated
several
facile
transformations
based
chloride
group
ester
group.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(17), С. 4197 - 4203
Опубликована: Июль 12, 2021
Abstract
The
first
organocatalytic
asymmetric
[4+3]‐cycloaddition
of
2‐aminophenyl
α,β‐unsaturated
carbonyls
with
in
situ
generated
azaoxyallyl
cations
was
developed,
and
enantioenriched
functionalized
seven‐membered
1,4‐benzodiazepine‐3‐ones
were
obtained
good
yields
excellent
enantioselectivities.
This
approach
also
extended
to
the
δ‐hydroxy
carbonyls,
affording
1,4‐oxazepanes
one
step
under
mild
conditions.
Several
novel
adducts
demonstrated
promising
bioactivity
prevention
peripheral
nerve
degeneration.
magnified
image
Abstract
This
review
introduces
the
synthetic
organic
chemical
value
of
α‐bromocarbonyl
compounds
with
tertiary
carbons.
compound
a
carbon
has
been
used
primarily
only
as
radical
initiator
in
atom
transfer
polymerization
(ATRP)
reactions.
However,
recent
development
photo‐radical
reactions
(around
2010),
research
on
use
alkyl
precursors
became
popular
2012).
As
more
examples
were
reported,
studied
not
radicals
but
also
for
their
applications
organometallic
and
ionic
That
is,
act
nucleophiles
well
electrophiles.
The
carbonyl
group
is
attractive
because
it
allows
skeleton
to
be
converted
after
reaction,
being
applied
total
synthesis.
In
our
survey
until
2022,
can
perform
full
range
necessary
synthesis,
including
multi‐component
reactions,
cross‐coupling,
substitution,
cyclization,
rearrangement,
stereospecific
asymmetric
α‐Bromocarbonyl
have
created
new
trend
alkylation,
which
then
had
limited
reaction
patterns
focuses
how
chemistry.
