Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(43)
Published: May 25, 2022
The
first
photo-mediated
process
enabling
the
generation
of
halide
radicals
by
Halogen-Atom
Transfer
(XAT)
is
described.
Contrary
to
radical
transformations
involving
XAT
reactivity,
which
exploit
stable
carbon
radicals,
this
unique
approach
uses
1,2-dihaloethanes
for
unstable
XAT.
These
transient
then
undergo
β-scission
with
release
ethylene
and
formation
more
have
been
used
in
selective
hydrohalogenations
a
large
number
unsaturated
hydrocarbons,
including
Michael
acceptors,
unactivated
alkenes
alkynes.
This
hydrohalogenation
tolerant
broad
range
functionalities
believed
proceed
through
radical-chain
manifold
that
propagates
use
silane
derivatives.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Jan. 28, 2022
Abstract
A
general
anti-Baldwin
radical
4-exo-dig
cyclization
from
nitrogen-substituted
alkynes
is
reported.
Upon
reaction
with
a
heteroleptic
copper
complex
in
the
presence
of
an
amine
and
under
visible
light
irradiation,
range
ynamides
were
shown
to
smoothly
cyclize
corresponding
azetidines,
useful
building
blocks
natural
product
synthesis
medicinal
chemistry,
full
control
regioselectivity
resulting
unique
underrated
pathway.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: April 8, 2023
Abstract
The
use
of
ynamides
in
organic
synthesis
has
gained
significant
attention
due
to
their
ability
provide
access
complex
molecular
structures
through
transformations
such
as
1,2‐difunctionalization
and
annulation
reactions.
These
reactions
enable
the
formation
highly
functionalized
N‐bearing
olefins
unusual
heterocycles.
In
this
minireview,
we
present
a
systematic
overview
regioselective
difunctionalization
ynamides.
We
discuss
multi‐component
reactions,
radical‐triggered
functionalizations
across
carbon–carbon
multiple
bonds
bifunctional
reagents
ynamides,
highlighting
potential
expanding
substrate
scope.
Furthermore,
insights
into
mechanistic
breakthroughs
that
have
been
achieved
recent
years
development
these
Finally,
emphasize
promising
future
prospects
versatile
building
blocks
for
architectures.
The Chemical Record,
Journal Year:
2021,
Volume and Issue:
21(12), P. 4123 - 4149
Published: Aug. 25, 2021
Ynamide,
a
unique
species
with
inherited
polarization
of
nitrogen
lone
pair
electron
to
triple
bond,
has
been
largely
used
for
the
developement
novel
synthetic
methods
and
construction
unusual
N-bearing
heterocycles.
The
reaction
versatility
ynamide
on
umpolung
reactivity,
radical
reactions
asymmetric
synthesis
have
recently
reviewed.
This
review
provides
an
overall
scenic
view
into
gold
catalyzed
transformation
ynamides.
ynamides
reactivity
towards
nitrogen-transfer
reagents,
such
as
azides,
ylides,
isoxazoles,
anthranils;
oxygen
atom-transfer
like
nitrones,
sulfoxides,
pyridine
N-oxides;
carbon
nucleophiles
under
catalysis
are
herein
uncovered.
scope
well
mechanistic
insights
each
is
also
briefed.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: April 29, 2022
The
radical
chemistry
of
ynamides
has
recently
drawn
the
attention
synthetic
organic
chemists
to
construction
various
N-heterocyclic
compounds.
Nevertheless,
ynamide-radical
remains
a
long-standing
challenge
for
due
its
high
reactivity,
undesirable
byproducts,
severe
inherent
regio-
and
chemoselective
problems.
Importantly,
ynamide
C(sp)-N
bond
fission
an
unsolved
challenge.
In
this
paper,
we
observe
Photoinduced
trigger
fission,
structural
reshuffling
functionalization
2-alkynyl-ynamides
prepare
synthetically
inaccessible/challenging
chalcogen-substituted
indole
derivatives
with
excellent
step/atom
economy.
key
breakthroughs
work
includes,
cleavage,
divergent
precursors,
broad
scope,
easy
handle,
larger-scale
reactions,
generation
multiple
bonds
(N-C(sp2),
C(sp2)-C(sp2),
C(sp2)-SO2R/C-SR,
C-I/C-Se/C-H)
in
few
minutes
without
photocatalysts,
metals,
oxidants,
additives.
Control
experiments
13C-labeling
supporting
conclusion
that
sulfone
radicals
contribute
processes
via
pathway.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(43), P. 6584 - 6587
Published: Jan. 1, 2023
We
synthesized
tetrasubstituted
olefins
regioselectively
and
stereoselectively
from
ynamides
internal
alkynes
with
sulfonyl
iodides
under
blue
LEDs
in
few
minutes.
The
key
features
are
being
metal-free,
easy
to
handle,
simple,
broad
scope,
environmentally
friendly.
Furthermore,
a
gram-scale
experiment
was
conducted,
the
corresponding
sulfonyl-iodinated
products
were
smoothly
altered
into
various
other
products.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(14), P. 2280 - 2298
Published: June 14, 2023
Abstract
Phosphonothioates,
phosphinothioates
and
phosphorothioates
are
regarded
as
an
important
class
of
sulfur‐containing
organophosphorus
compounds.
Because
the
unique
P(O)S−R
group,
these
compounds
have
biological
activities
thus
been
widely
used
in
fields
pharmaceuticals
pesticides.
In
recent
years,
development
by
radical
processes
has
attracted
considerable
attention
chemistry.
Along
lines,
this
review,
advances
synthesis
were
systematically
summarized.
According
to
different
ways
generating
radicals
during
formation
process
phosphonothioates,
phosphorothioates,
transformations
can
be
divided
into
four
categories:
(1)
Oxidant
or
metal‐free
promoted
transformation
fabricate
compounds;
(2)
Copper‐catalyzed
produce
(3)
Photo‐induced
prepare
(4)
Electro‐induced
derive
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(4), P. 2190 - 2199
Published: Jan. 27, 2024
Ketenimines
represent
an
important
class
of
reactive
species,
useful
synthetic
intermediates,
and
synthons.
However,
in
general,
ketenimines
preferentially
undergoes
nucleophilic
addition
reactions
with
hydroxyl
amino
groups,
carbon
functional
groups
remain
a
less
studied
subset
such
systems.
Herein,
we
develop
straightforward
syntheses
pyridin-4(1H)-imines
that
is
achieved
by
cyclization
reacting
enaminone
unit
α-acylketenimine
which
generated
from
the
sulfonyl
azides
terminal
ynones
situ
(CuAAC/Ring
cleavage
reaction).
The
cascade
process
starts
α-C
instead
group,
attacking
electron-deficient
central
ketenimine,
chemoselectivity
unconventional
products
were
formed
intramolecular
cyclization.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(43), P. 5254 - 5257
Published: Jan. 1, 2021
The
first
photoinduced
synthesis
of
polyfunctionalized
3-aza[n.1.0]bicycles
from
readily
available
ene-ynamides
and
2,6-lutidine
N-oxide
using
an
organic
acridinium
photocatalyst
is
reported.
