Communications Chemistry,
Год журнала:
2024,
Номер
7(1)
Опубликована: Июнь 19, 2024
Abstract
Radical-polar
crossover
of
organoborates
is
a
poweful
tool
that
enables
the
creation
two
C-C
bonds
simultaneously.
Small
ring
systems
have
become
essential
motifs
in
drug
discovery
and
medicinal
chemistry.
However,
step-economic
methods
for
their
selective
functionalization
remains
scarce.
Here
we
present
one-pot
strategy
merges
simple
preparation
strained
organoboron
species
with
recently
popularized
polar
radical
borate
derivatives
to
stereoselectively
access
tri-substituted
azetidines,
cyclobutanes
five-membered
carbo-
heterocycles.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15360 - 15369
Опубликована: Июль 10, 2023
Azetidines
are
prominent
structural
scaffolds
in
bioactive
molecules,
medicinal
chemistry,
and
ligand
design
for
transition
metals.
However,
state-of-the-art
methods
cannot
be
applied
to
intramolecular
hydroamination
of
allylic
amine
derivatives
despite
their
underlying
potential
as
one
the
most
prevalent
synthetic
precursors
azetidines.
Herein,
we
report
an
electrocatalytic
method
sulfonamides
access
azetidines
first
time.
The
merger
cobalt
catalysis
electricity
enables
regioselective
generation
key
carbocationic
intermediates,
which
could
directly
undergo
C-N
bond
formation.
mechanistic
investigations
including
electrochemical
kinetic
analysis
suggest
that
either
catalyst
regeneration
by
nucleophilic
cyclization
or
second
oxidation
intermediate
is
involved
rate-determining
step
(RDS)
our
protocol
highlight
ability
electrochemistry
providing
ideal
means
mediate
oxidation.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(8)
Опубликована: Дек. 28, 2022
The
synthesis
of
four
membered
heterocycles
usually
requires
multi-step
procedures
and
prefunctionalized
reactants.
A
straightforward
alternative
is
the
photochemical
[2+2]-heterocycloaddition
between
an
alkene
a
carbonyl
derivative,
conventionally
based
on
photoexcitation
this
latter.
However,
approach
limited
by
absorption
profile
carbonyl,
requiring
in
most
cases
use
high-energy
UV-light,
that
often
results
undesired
side
reactions
and/or
degradation
reaction
components.
development
new
milder
visible
light-driven
[2+2]-heterocycloadditions
is,
therefore,
highly
desirable.
In
Review,
we
highlight
relevant
achievements
promoted
light,
with
particular
emphasis
involved
mechanisms.
open
challenges
will
also
be
discussed,
suggesting
possible
evolutions,
stimulating
methodological
developments
field.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июль 3, 2023
Abstract
The
synthesis
of
polycyclic
compounds
is
high
interest
due
to
the
prevalence
these
motifs
in
drugs
and
natural
products.
Herein,
we
report
on
stereoselective
construction
3D
bicyclic
scaffolds
azetidine
derivatives
by
modulation
N
‐sulfonylimines
achieve
either
[4+2]‐
or
[2+2]‐cycloaddition
reactions.
utility
method
was
established
further
product.
Mechanistic
studies
are
also
included,
which
support
reaction
via
Dexter
energy
transfer.
Science,
Год журнала:
2024,
Номер
384(6703), С. 1468 - 1476
Опубликована: Июнь 27, 2024
The
aza
Paternò-Büchi
reaction
is
a
[2+2]-cycloaddition
between
imines
and
alkenes
that
produces
azetidines,
four-membered
nitrogen-containing
heterocycles.
Currently,
successful
examples
rely
primarily
on
either
intramolecular
variants
or
cyclic
imine
equivalents.
To
unlock
the
full
synthetic
potential
of
reactions,
it
essential
to
extend
acyclic
Here,
we
report
matching
frontier
molecular
orbital
energies
with
those
oximes
enables
visible
light-mediated
reactions
through
triplet
energy
transfer
catalysis.
utility
this
further
showcased
in
synthesis
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(41), С. 19089 - 19096
Опубликована: Окт. 5, 2022
Despite
their
favorable
properties,
azetidines
are
often
overlooked
as
lead
compounds
across
multiple
industries.
This
is
attributed
to
the
challenging
synthesis
of
densely
functionalized
in
an
efficient
manner.
In
this
work,
we
report
scalable
and
characterization
seven
with
varying
regio-
stereochemistry
application
novel
azetidine-based
energetic
materials,
enabled
by
visible-light-mediated
aza
Paternò-Büchi
reaction.
The
performance
stark
differences
physical
properties
these
new
make
them
excellent
potential
candidates
solid
melt-castable
explosive
well
liquid
propellant
plasticizers.
work
highlights
scalability
utility
visible-light
reaction
demonstrates
impact
stereochemical
considerations
on
energetics.
Considering
versatility
efficiency
presented
synthetic
strategies,
expect
that
will
guide
development
materials
energetics
space
other
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(21), С. 3556 - 3571
Опубликована: Авг. 2, 2023
Abstract
Harnessing
visible
light
to
trigger
(aza
and
thia)
Paternò‐Büchi
reaction
injects
new
vitality
into
[2+2]
photocyclization
enable
impressive
reactivity
modes.
The
popular
is
one
of
the
most
efficient
ways
synthesize
strained
four‐membered
heterocycles.
Recently,
visible‐light‐triggered
reactions
have
received
considerable
attentions
as
this
strategy
has
overcome
some
long‐standing
challenges,
remarkable
achievements
been
made
within
field.
Strained
heterocyclics
with
favorable
properties
provide
a
perfect
combination
stable
skeletons
for
pharmaceutical
chemistry
intermediates
further
transformation.
In
review,
we
highlight
recent
advances
in
an
emphasis
on
mechanism
applications.
Organization
review
follows
subdivision
according
type
substrate
classes.
