Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon‐carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo‐Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring‐opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
2
insertion
into
α,β
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
provides
further
tool
for
modification
carbon
framework
organic
compounds,
complementing
recent
progress
“skeletal
editing”.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18565 - 18575
Опубликована: Июнь 27, 2024
Bridged
bicyclic
scaffolds
are
emerging
bioisosteres
of
planar
aromatic
rings
under
the
concept
"escape
from
flatland".
However,
adopting
this
into
exploration
pyridines
remains
elusive
due
to
challenge
incorporating
a
N
atom
such
bridged
structures.
Herein,
we
report
practical
routes
for
divergent
synthesis
2-
and
3-azabicyclo[3.1.1]heptenes
(aza-BCHepes)
as
potential
readily
accessible
vinyl
azides
bicyclo[1.1.0]butanes
(BCBs)
via
two
distinct
catalytic
annulations.
The
reactivity
tailored
with
BCBs
is
key
achieving
transformations.
Ti
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(5)
Опубликована: Фев. 21, 2024
Abstract
Within
a
medicinal
chemist's
toolbox,
one
of
the
most
effective
strategies
to
improve
overall
properties
biologically
active
compound
is
bioisosteric
replacement.
Ever
since
first
example
replacing
benzene
with
bicyclo[1.1.1]pentane
(BCP)
group
was
published
in
late
1990s,
[1]
chemistry
community
has
continually
been
expanding
scope
such
phenyl
replacements.
Recent
interest
from
academia
focused
on
novel
synthetic
access
C(
sp
3
)‐rich
bicyclic
hydrocarbons
expanded
ring
sizes.
Herein,
we
summarize
some
these
transformations
and
reveal
that
rely
strain
releasing
cycloadditions
bicyclo[1.1.0]butane
(BCB)
bicyclo[2.1.0]pentane
(housane).
We
have
organized
this
review
based
mechanism
release
strategies,
namely,
carbene
cycloadditions,
energy
transfer
photocatalyzed
electron
catalyzed
polar
cycloadditions.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 19, 2024
Saturated
nitrogen
heterocycles
are
among
the
most
significant
structural
components
in
small-molecule
pharmaceuticals.
Herein,
a
protocol
for
construction
of
enantiopure
2-azabicyclo[3.1.1]heptane
derivatives
by
stereospecific
intermolecular
formal
cycloaddition
aziridines
with
bicyclo[1.1.0]butanes
is
described.
The
reaction
run
using
B(C
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(46), С. 31400 - 31404
Опубликована: Ноя. 7, 2024
Bicyclo[2.1.1]hexanes
have
emerged
as
valuable
scaffolds
for
the
design
of
new
pharmaceutical
and
agrochemical
active
ingredients.
These
structures
can
be
efficiently
synthesized
via
[2π
+
2σ]
photocycloadditions;
however,
control
over
absolute
stereochemistry
these
strain-releasing
reactions
has
remained
challenging.
Herein,
we
demonstrate
that
Brønsted
acid
catalyzed
chromophore
activation
C-acyl
imidazoles
enables
highly
enantioselective
photocycloadditions.
Because
this
approach
is
agnostic
to
identity
coupling
partner,
same
strategy
used
synthesize
several
other
medicinally
relevant
strained
small-ring
structures.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
Rigid
bicyclic
hydrocarbons
have
emerged
as
important
building
blocks
in
the
drug
discovery
industry.
Despite
progress
this
general
area,
bicyclo[2.1.0]pentanes
(housanes)
are
an
understudied
class
of
molecules.
Herein
we
report
unconventional
synthesis
borylated
housanes.
Our
method
features
a
broad
scope
and
high
diastereoselectivities
versatile
intermediates.
The
route
involves
strain-release
diboration
bicyclo[1.1.0]butane
intramolecular
deborylative
alkylation.
versatility
bridgehead
boronic
ester
was
demonstrated
several
functionalizations.
Lastly,
mechanism
reaction
investigated,
unusual
stereospecific
diastereoselective
ring
expansion
uncovered.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 6, 2025
Cyclopropylamines
are
an
important
subclass
of
substituted
cyclopropanes
that
combine
the
unique
electronic
and
steric
properties
with
presence
a
donor
nitrogen
atom.
In
addition
to
their
in
diverse
array
biologically
active
compounds,
cyclopropylamines
utilized
as
synthetic
intermediates,
particularly
ring-opening
or
cycloaddition
reactions.
Consequently,
synthesis
these
compounds
has
constituted
significant
research
topic,
evidenced
by
abundant
published
methods.
widely
used
Curtius
rearrangement,
classical
cyclopropanation
methods
have
been
adapted
integrate
function
(Simmons-Smith
reaction,
metal-catalyzed
reaction
diazo
on
olefins,
Michael-initiated
ring-closure
reactions)
advances
enantioselective
synthesis.
More
recently,
specific
developed
for
preparation
aminocyclopropane
moiety
(Kulinkovich
reactions
applied
amides
nitriles,
cyclopropenes,
involving
C-H
functionalization,
...).
The
topic
this
review
is
present
different
cyclopropylamine
derivatives,
aim
covering
methodological
best
possible,
highlighting
scope,
stereochemical
aspects
future
trends.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(44)
Опубликована: Июль 22, 2024
Abstract
C(sp
3
)‐rich
heterocycles
are
privileged
building
blocks
for
pharmaceuticals
and
agrochemicals.
Therefore,
synthetic
methods
that
provide
access
to
novel
saturated
nitrogen‐containing
in
high
demand.
Herein,
we
report
a
general
synthesis
of
1‐azabicyclo[2.1.1]hexanes
(1‐aza‐BCH)
via
formal
cycloaddition
azabicyclo[1.1.0]butanes
(ABB)
with
styrenes
under
photochemical
conditions.
To
overcome
the
challenging
direct
single
electron
reduction
ABBs,
designed
polar‐radical‐polar
relay
strategy
leverages
fast
acid‐mediated
ring‐opening
ABBs
form
bromoazetidines,
which
undergo
efficient
debrominative
radical
formation
initiate
reaction.
The
reaction
is
applicable
broad
range
ABB‐ketones
demonstrate
1‐aza‐BCH
products
can
be
further
functionalized
larger
saturated,
conformationally
rigid
heterocycles.
