Angewandte Chemie,
Год журнала:
2024,
Номер
136(46)
Опубликована: Июль 12, 2024
Abstract
The
synthesis
of
housane
derivatives
from
cyclopropenes
is
described.
Under
rhodium(II)
catalysis,
cyclopropenylvinyl
carbinols
can
regioselectively
generate
a
carbene
intermediate
which
undergoes
an
intramolecular
cyclopropanation
to
form
housane,
skeleton
with
similar
ring
strain
as
the
cyclopropene
precursor.
procedure
shows
remarkable
broad
scope
and
efficiency.
Moreover,
method
served
prepare
man‐made
housane‐containing
terpene
derivatives,
are
not
accessible
by
Nature.
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.
This
study
describes
a
method
for
the
stereoselective
synthesis
of
highly
functionalized
bicyclo[2.1.0]pentanes
(housanes).
The
approach
utilizes
two-step
sequence,
silver-
or
gold-catalyzed
cyclopropenation
alkynes
followed
by
an
intermolecular
[2
+
2]
photocycloaddition
reaction
with
electron-deficient
alkenes.
is
established
aryldiazoacetates.
A
regioselective
cycloaddition
cyclopropane
was
developed
using
blue
LED
irradiation,
commercially
available
photocatalyst
as
triplet-sensitizer,
and
low
temperature
(−40
°C).
diastereoselective,
when
enantioenriched
cyclopropenes
are
used,
it
proceeds
enantioretention.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(46)
Опубликована: Июль 12, 2024
Abstract
The
synthesis
of
housane
derivatives
from
cyclopropenes
is
described.
Under
rhodium(II)
catalysis,
cyclopropenylvinyl
carbinols
can
regioselectively
generate
a
carbene
intermediate
which
undergoes
an
intramolecular
cyclopropanation
to
form
housane,
skeleton
with
similar
ring
strain
as
the
cyclopropene
precursor.
procedure
shows
remarkable
broad
scope
and
efficiency.
Moreover,
method
served
prepare
man‐made
housane‐containing
terpene
derivatives,
are
not
accessible
by
Nature.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
this
paper,
we
describe
a
new
type
of
cross-coupling
between
simple
diazo
and
vinyldiazo
compounds
that
gives
access
to
unusual
allyldiazo
products.
Blue
light
discriminates
two
towards
free
carbene
formation,
triggering
sequential
cyclopropenation,
(3+2)
cycloaddition
ring
opening
rearrangement
processes.
This
strategy
involves
an
overall
reshuffle
functionality
olefinic
carbons
with
extrusion
nitrogen.
Mechanistic
studies
including
15N-labelling
experiment
demonstrate
the
products
derives
from
compounds,
while
reagents
are
selectively
decomposed
via
energy
transfer
thioxanthone
photocatalyst.
The
obtained
can
be
efficiently
converted
into
synthetically
useful
structures
such
as
1,3-dienes,
gem-difluoro-1,4-diene,
hydrazine,
dihydropyrazole,
pyridazine,
bicyclobutane.
The Chemical Record,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
Abstract
Organofluorine
compounds
are
of
pivotal
significance
particularly,
in
drug
and
agrochemical
industries
different
strategies
have
been
designed
for
their
synthesis.
The
last
two
decades
witnessed
the
emergence
difluorocarbene
as
an
efficient
synthetic
tool,
providing
easy
access
to
organofluorine
compounds.
This
review
summarises
reactions
generated
from
Ruppert‐Prakash
reagent
(TMSCF
3
)
its
derivatives
TMSCF
2
Cl
Br.
Among
various
fluorination
techniques
available,
chemistry
offers
a
cost
effective
procedure,
opening
avenue
large
number
details
developments
utility
derivatives,
till
date.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 18, 2025
The
Alder-ene
reaction
of
the
C-C
bond
in
bicyclo[1.1.0]butanes
would
provide
a
unique
and
efficient
synthesis
route
for
cyclobutene
frameworks.
Herein,
we
report
regio-
diastereoselective
with
β-fluoroalkyl-α,β-unsaturated
ketones,
giving
wide
variety
cyclobutenes
two
contiguous
centers
diene
products.
features
atoms
step
economies
exhibits
broad
substrate
scope.
Several
downstream
transformations
these
were
performed.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(33), С. 18591 - 18597
Опубликована: Авг. 8, 2023
Herein,
we
demonstrate
the
use
of
E/Z
mixtures
α,α-disubstituted
crotylhydrazones
to
obtain
spirocyclic
vinylcyclobutanes
in
a
diastereoselective
fashion.
We
show
24
examples
1,1-insertion/4-exo-trig
tandem
process
produce
these
motifs.
Additionally,
alkylidene
cyclobutanes
can
be
obtained
by
using
allylated
hydrazones
(11
examples).
In
this
study,
that
aryl
migrating
group
has
dramatic
impact
on
course
reaction.
Specifically,
allylic
C-H
insertion
products
good
yields
bromoenones
as
reaction
partners.
When
Pd(0)
is
used
with
no
or
alkenyl
bromide,
an
intramolecular
cyclopropanation
takes
place
afford
[2.1.0]-bicycles.
