Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(14)
Опубликована: Янв. 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.
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
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Май 11, 2024
Abstract
The
exploration
of
the
complex
chemical
diversity
bicyclo[n.1.1]alkanes
and
their
use
as
benzene
bioisosteres
has
garnered
significant
attention
over
past
two
decades.
Regiodivergent
syntheses
thiabicyclo[4.1.1]octanes
(S‐BCOs)
highly
substituted
bicyclo[2.1.1]hexanes
(BCHs)
using
a
Lewis
acid‐catalyzed
formal
cycloaddition
bicyclobutanes
(BCBs)
3‐benzylideneindoline‐2‐thione
derivatives
have
been
established.
first
hetero‐(4+3)
BCBs,
catalyzed
by
Zn(OTf)
2
,
was
achieved
with
broad
substrate
scope
under
mild
conditions.
In
contrast,
less
electrophilic
BCB
ester
undergoes
Sc(OTf)
3
‐catalyzed
[2π+2σ]
reaction
1,1,2‐trisubstituted
alkenes,
yielding
BCHs
spirocyclic
quaternary
carbon
center.
Control
experiments
preliminary
theoretical
calculations
suggest
that
diastereoselective
product
formation
may
involve
concerted
between
zwitterionic
intermediate
E
‐1,1,2‐trisubstituted
alkenes.
Additionally,
nucleophilic
ring‐opening
mechanism.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(14)
Опубликована: Янв. 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.
