ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12225 - 12233
Опубликована: Авг. 1, 2024
Skipped
dienes
are
not
only
present
in
fatty
acid
primary
metabolites
and
natural
products
but
also
serve
as
reactive
intermediates
diverse
chemical
synthesis.
Despite
this,
the
regioselective
stereoselective
synthesis
of
skipped
remains
a
challenging
goal.
Strain
release
organic
molecules
is
powerful
tool
for
creating
complexity
under
mild
conditions.
The
reactivity
strained
bicyclo[1.1.0]butane
(BCB)
systems
mainly
dominated
by
transformations
relying
on
their
innate
electrophilic
reactivity.
Herein,
we
report
rare
example
carbene-type
BCB
system
based
rhodium–carbene
chemistry,
which
enables
highly
through
strain
release.
reaction
compatible
with
range
functional
groups
both
diazo
compounds
BCBs
could
be
applied
successfully
to
complex
structures,
providing
valuable
functionalizable
dienes.
introduced
during
served
synthetic
handles
downstream
manipulations.
high
stereoselectivity
observed
has
been
rationalized
DFT
calculations,
suggests
that
likely
proceeding
via
concerted
mechanism,
noncovalent
interactions
between
metallocarbene
control
exclusive
selectivity.
Tetrahedron Chem,
Год журнала:
2024,
Номер
9, С. 100070 - 100070
Опубликована: Фев. 28, 2024
Bicyclo[1.1.0]butanes
(BCBs)
and
[1.1.1]propellanes
(tricyclo[1.1.1.01,3]pentanes,
TCPs)
are
structurally
unique
compounds
with
different
chemical
properties.
Strain-release
driven
reactions
have
emerged
as
an
atom-
step-economic
strategy
for
the
organic
synthesis.
Using
this
strategy,
a
variety
of
functional
ring
molecules
been
efficiently
synthesized,
including
various
cyclobutane
molecules,
bicyclo[2.1.1]hexanes,
bicyclo[1.1.1]pentanes,
others.
More
specifically,
these
strain
release-driven
include
aspects
nucleophilic
addition,
radical
electrophilic
or
transition
metal
catalysis.
This
review
will
discuss
recent
developments
in
strain-release
transformations
bicyclo[1.1.0]butanes
[1.1.1]propellanes.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 2073 - 2078
Опубликована: Март 6, 2024
A
visible-light-induced
radical
alkylarylation
of
N-aryl
bicyclobutyl
amides
with
α-carbonyl
alkyl
bromides
for
the
synthesis
functionalized
3-spirocyclobutyl
oxindoles
is
described
in
which
β-selective
addition
to
forms
a
key
intermediate
followed
by
interception
intrinsic
arene
functional
group.
This
approach
can
be
applicable
wide
range
bromides,
including
primary,
secondary,
and
tertiary
α-bromoalkyl
esters,
ketones,
nitriles,
nitro
compounds.
Chemical Science,
Год журнала:
2024,
Номер
15(31), С. 12473 - 12479
Опубликована: Янв. 1, 2024
Bicyclo[1.1.0]butanes
(BCBs),
featuring
two
fused
cyclopropane
rings,
have
found
widespread
application
in
organic
synthesis.
Their
versatile
reactivity
towards
radicals,
nucleophiles,
cations,
and
carbenes
makes
them
suitable
for
various
reactions,
including
ring-opening
annulation
strategies.
Despite
this
versatility,
their
potential
as
enophiles
an
ene
reaction
remains
underexplored.
Considering
given
the
challenges
of
achieving
diastereoselectivity
reactions
BCBs,
herein,
we
present
a
unique
method
utilizing
BCBs
mild
diastereoselective
Sc(OTf)
A
metal-free
photosensitized
1,2-imino-thiocyanation
of
olefins
has
been
established
by
using
the
easily
accessible
bifunctional
reagent
S-cyano-N-(diphenylmethylene)
thiohydroxylamine.
wide
range
were
successfully
transformed
into
corresponding
β-iminothiocyanates
in
moderate
to
high
yields.
This
protocol
stands
out
for
its
nature,
broad
substrate
compatibility,
and
atom
step
economy,
providing
an
effective
strategy
assembling
β-amino
thiocyanate-containing
scaffolds.
The
exploration
of
C(sp3)-rich
three-dimensional
(3D)
scaffolds
as
bioisosteres
for
planar
aromatics
has
garnered
increasing
attention.
While
the
bioisosterism
benzenes
been
extensively
studied,
pyridines,
second
most
prevalent
aromatic
compounds
in
pharmaceuticals,
faces
additional
challenges
and
encountered
surprisingly
limited
success.
In
this
study,
we
propose
unprecedented
2-azabicyclo[3.1.1]heptenes
effective
1,3,5-trisubstituted
pyridines
terms
not
only
3D
conformation
but
also
basicity.
We
develop
a
pyridine-boryl
radical-catalyzed
[3π
+
2σ]
cycloaddition
reaction
vinyl
azides
with
bicyclo[1.1.0]butanes
(BCBs)
an
efficient
synthetic
approach.
Synthetic
manipulation
products
reveals
valuable
handles,
allowing
modular
synthesis
various
pyridine
bioisosteres.
Green Chemistry,
Год журнала:
2024,
Номер
26(9), С. 5512 - 5518
Опубликована: Янв. 1, 2024
Photochemical
solvent-controlled
difluoromethylation
and
bromo-difluoromethylation
reactions
of
bicyclobutanes
are
described.
The
method
provides
efficient
pathways
to
obtain
difluoroalkyl
functionalized
bioisosteres
for
drug
discovery.
