Chemical Science,
Год журнала:
2024,
Номер
15(46), С. 19488 - 19495
Опубликована: Янв. 1, 2024
We
present
the
first
enantioselective
dearomative
(3+3)
cycloadditions
of
bicyclobutanes
(BCBs)
utilizing
a
chiral
Lewis
acid
catalyst
and
bidentate
chelating
BCB
substrates.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 19621 - 19628
Опубликована: Май 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.
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(32)
Опубликована: Май 24, 2024
Abstract
Synthesis
of
bicyclic
scaffolds
has
gained
significant
attention
in
drug
discovery
due
to
their
potential
mimic
benzene
bioisosteres.
Here,
we
present
a
mild
and
scalable
Sc(OTf)
3
‐catalyzed
[3+2]
cycloaddition
bicyclo[1.1.0]butanes
(BCBs)
with
ynamides,
yielding
diverse
array
polysubstituted
2‐amino‐bicyclo[2.1.1]hexenes
good
excellent
yields.
These
products
offer
valuable
starting
materials
for
the
construction
novel
functionalized
bicyclo[1.1.0]butanes.
Preliminary
mechanistic
studies
indicate
that
reaction
involves
nucleophilic
addition
ynamides
bicyclo[1.1.0]butanes,
followed
by
an
intramolecular
cyclization
situ
generated
enolate
keteniminium
ion.
We
expect
these
findings
will
encourage
utilization
complex
bioisosteres
foster
further
investigation
into
BCB‐based
chemistry.
Organic Letters,
Год журнала:
2024,
Номер
26(19), С. 4104 - 4110
Опубликована: Май 3, 2024
Herein,
a
B(C6F5)3-catalyzed
formal
(n
+
3)
=
5
and
6)
cycloaddition
of
bicyclo[1.1.0]butanes
(BCBs)
with
imidazolidines/hexahydropyrimidines
is
described.
The
reaction
provides
modular,
atom-economical,
efficient
strategy
to
two
libraries
synthetically
challenging
medium-bridged
rings,
2,5-diazabicyclo[5.1.1]nonanes
2,6-diazabicyclo[6.1.1]decanes,
in
moderate
excellent
yields.
This
also
features
simple
operation,
mild
conditions,
broad
substrate
scope.
A
scale-up
experiment
various
synthetic
transformations
products
further
highlight
the
utility.
Chemical Science,
Год журнала:
2024,
Номер
15(28), С. 10823 - 10829
Опубликована: Янв. 1, 2024
Bicyclo[4.1.1]octanes
(BCOs)
were
synthesized
in
up
to
quantitative
yields
through
the
formal
[4+2]
cycloaddition
of
aryl
and
alkyl
bicyclobutane
(BCB)
ketones
with
dienol
silyl
ethers
using
Al(OTf)
3
as
a
Lewis
acid
catalyst.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 25, 2024
The
selective
construction
of
bridged
bicyclic
scaffolds
has
garnered
increasing
attention
because
their
extensive
use
as
saturated
bioisosteres
arene
in
pharmaceutical
industry.
However,
sharp
contrast
to
racemic
counterparts,
assembling
chiral
structures
an
enantioselective
and
regioselective
manner
remains
challenging.
Herein,
we
describe
our
protocol
for
constructing
2-oxa-3-azabicyclo[3.1.1]heptanes
(BCHeps)
by
[4π
+
2σ]
cycloadditions
bicyclo[1.1.0]butanes
(BCBs)
nitrones
taking
advantage
a
copper(II)
complex
Lewis
acid
catalyst.
This
method
features
mild
conditions,
good
functional
group
tolerance,
high
yield
(up
99%),
excellent
enantioselectivity
99%
ee).
Density
theory
(DFT)
calculation
elucidates
the
origin
reaction's
mechanism
BCB
activation
Cu(II)
complex.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 20, 2024
Abstract
Saturated
three-dimensional
carbocycles
have
gained
increasing
prominence
in
synthetic
and
medicinal
chemistry.
In
particular,
bicyclo[2.1.1]hexanes
(BCHs)
been
identified
as
the
molecular
replacement
for
benzenes.
Here,
we
present
facile
access
to
a
variety
of
BCHs
via
stepwise
two-electron
formal
(3
+
2)
cycloaddition
between
silyl
enol
ethers
bicyclo[1.1.0]butanes
(BCBs)
under
Lewis
acid
catalysis.
The
reaction
features
wide
functional
group
tolerance
ethers,
allowing
efficient
construction
two
vicinal
quaternary
carbon
centers
silyl-protected
tertiary
alcohol
unit
streamlined
fashion.
Interestingly,
with
conjugated
dienol
can
provide
bicyclo[4.1.1]octanes
(BCOs)
equipped
that
facilitate
further
transformation.
utilities
this
methodology
are
demonstrated
by
late-stage
modification
natural
products,
transformations
units
on
bicyclo[2.1.1]hexane
frameworks,
derivatization
bicyclo[4.1.1]octanes,
delivering
functionalized
bicycles
traditionally
inaccessible.