Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(18), P. 3112 - 3117
Published: July 26, 2023
Abstract
Herein,
a
visible
light‐mediated
multicomponent
radical
cross‐coupling
reaction
of
[1.1.1]propellane
with
N
‐heterocycles
and
disulfides
is
described.
The
mild
conditions
enabled
the
installation
BCP
motif
in
wide
variety
compounds
absence
photocatalyst,
additive
metal
catalyst,
excellent
functional
group
tolerance,
This
methodology
opens
approach
for
synthesis
potentially
bioactive
1‐arylthiol‐3‐heteroaryl
bicyclo[1.1.1]pentanes
moderate
to
good
yield.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(3), P. 1068 - 1089
Published: Jan. 1, 2024
Leveraging
light
energy
to
expose
the
‘dark’
reactive
states
describes
whole
essence
of
triplet–triplet
transfer.
This
offers
an
impressive
opportunity
conduct
a
multitude
diverse
reactions
and
access
sought-after
molecular
motifs.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(38), P. 20716 - 20732
Published: Sept. 15, 2023
The
concept
of
strain
in
organic
compounds
is
as
old
modern
chemistry
and
was
initially
introduced
to
justify
the
synthetic
setbacks
along
synthesis
small
ring
systems
(pars
construens
strain).
In
last
decades,
chemists
have
developed
an
arsenal
strain-release
reactions
destruens
strain)
which
can
generate─with
significant
driving
force─rigid
aliphatic
that
act
three-dimensional
alternatives
(hetero)arenes.
Photocatalysis
added
additional
dimension
processes
by
leveraging
energy
photons
create
chemical
complexity
under
mild
conditions.
This
perspective
presents
latest
advancements
photocatalysis─with
emphases
on
mechanisms,
catalytic
cycles,
current
limitations─the
unique
architectures
be
produced,
possible
future
directions.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(48)
Published: Oct. 12, 2023
Bicyclo[2.1.1]hexanes
(BCHs)
are
becoming
ever
more
important
in
drug
design
and
development
as
bridged
scaffolds
that
provide
underexplored
chemical
space,
but
difficult
to
access.
Here
a
silver-catalyzed
dearomative
[2π+2σ]
cycloaddition
strategy
for
the
synthesis
of
indoline
fused
BCHs
from
N-unprotected
indoles
bicyclobutane
precursors
is
described.
The
strain-release
operates
under
mild
conditions,
tolerating
wide
range
functional
groups.
It
capable
forming
with
up
four
contiguous
quaternary
carbon
centers,
achieving
yields
99
%.
In
addition,
scale-up
experiment
synthetic
transformations
cycloadducts
further
highlighted
utility.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 8372 - 8380
Published: March 18, 2024
Here
we
present
a
highly
enantioselective
[2π
+
2σ]
photocycloaddition
of
bicyclo[1.1.0]butanes
(BCBs).
The
reaction
uses
variety
vinylazaarenes
as
partners
and
is
catalyzed
by
polycyclic
aromatic
hydrocarbon
(PAH)-containing
chiral
phosphoric
acid
bifunctional
photosensitizer.
A
wide
array
pharmaceutically
important
bicyclo[2.1.1]hexane
(BCH)
derivatives
have
been
synthesized
with
high
yields,
enantioselectivity,
diastereoselectivity.
In
addition
to
the
diverse
1-ketocarbonyl-3-substituted
BCBs,
α/β-substituted
are
compatible
such
an
unprecedented
photoredox
catalytic
pathway,
resulting
in
successful
assembly
all-carbon
quaternary
stereocenter
or
two
adjacent
tertiary
stereocenters
on
product.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(29), P. 19621 - 19628
Published: May 13, 2024
For
nearly
60
years,
significant
research
efforts
have
been
focused
on
developing
strategies
for
the
cycloaddition
of
bicyclobutanes
(BCBs).
However,
higher-order
and
catalytic
asymmetric
BCBs
long-standing
formidable
challenges.
Here,
we
report
Pd-catalyzed
ligand-controlled,
tunable
cycloadditions
divergent
synthesis
bridged
bicyclic
frameworks.
The
dppb
ligand
facilitates
formal
(5+3)
vinyl
oxiranes,
yielding
valuable
eight-membered
ethers
with
scaffolds
in
100%
regioselectivity.
Cy-DPEphos
promotes
selective
hetero-[2σ+2σ]
to
access
pharmacologically
important
2-oxabicyclo[3.1.1]heptane
(O-BCHeps).
Furthermore,
corresponding
O-BCHeps
94–99%
ee
has
achieved
using
chiral
(S)-DTBM-Segphos,
representing
first
cross-dimerization
two
strained
rings.
obtained
are
promising
bioisosteres
ortho-substituted
benzenes.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Jan. 10, 2024
Abstract
Bioisosteric
design
has
become
an
essential
approach
in
the
development
of
drug
molecules.
Recent
advancements
synthetic
methodologies
have
enabled
rapid
adoption
this
strategy
into
discovery
programs.
Consequently,
conceptionally
innovative
practices
would
be
appreciated
by
medicinal
chemistry
community.
Here
we
report
expeditous
method
for
synthesizing
aryl
difluoromethyl
bicyclopentane
(ADB)
as
a
bioisostere
benzophenone
core.
This
involves
merger
light-driven
C−F
bond
activation
and
strain-release
under
catalysis
newly
designed
N
-anionic-based
organic
photocatalyst.
defluorinative
coupling
methodology
enables
direct
conversion
wide
variety
commercially
available
trifluoromethylaromatic
bonds
(more
than
70
examples)
corresponding
bicyclo[1.1.1]pentanes
(BCP)
arenes/difluoromethyl
BCP
boronates
single
step.
The
can
also
applied
to
[3.1.1]and
[4.1.1]propellane
systems,
providing
access
analogues
with
different
geometries.
Moreover,
successfully
used
protocol
rapidly
prepare
ADB-substituted
bioactive
molecule
Adiporon.
Biological
testing
shown
that
ADB
scaffold
potential
enhance
pharmacological
properties
benzophenone-type
candidates.
Asian Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
13(5)
Published: Feb. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(14)
Published: Jan. 5, 2024
Bicycloalkanes,
cubanes
and
their
structural
analogues
have
emerged
as
bioisosteres
of
(hetero)arenes.
To
meet
increasing
demand,
the
chemical
community
has
developed
a
plethora
novel
synthetic
methods.
In
this
review,
we
assess
progress
made
in
field
light-driven
construction
functionalization
such
relevant
molecules.
We
focused
on
diverse
targets,
well
reaction
processes
giving
access
to:
(i)
[1.1.1]-bicyclopentanes
(BCPs);
(ii)
[2.2.1]-bicyclohexanes
(BCHs);
(iii)
[3.1.1]-bicycloheptanes
(BCHeps);
(iv)
cubanes;
other
structurally
related
scaffolds.
Finally,
future
perspectives
dealing
with
identification
manifolds
to
new
functionalized
bioisosteric
units
are
discussed.
