Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 12, 2024
Abstract
Enantioselective
synthesis
of
(spiro)cyclobutane
derivatives
poses
significant
challenges
yet
holds
promising
applications
for
both
synthetic
and
medicinal
chemistry.
We
report
here
a
nickel‐catalyzed
asymmetric
syn
‐hydrometalative
4‐
exo
‐
trig
cyclization
1,4‐alkynones
to
synthesize
alkenyl
cyclobutanols
with
tetrasubstituted
stereocenter.
This
strategy
features
broad
substrate
scope,
delivering
variety
trifluoromethyl‐containing
rigid
(spiro)carbocycle
skeletons
in
good
yields
high
enantioselectivities
(up
84
%
yield
98.5
:
1.5
er).
The
utility
is
demonstrated
through
stereospecific
transformations
into
fused
spiro
molecules.
Experimental
computational
mechanistic
studies
indicate
that
the
reaction
initiated
by
an
active
Ni−H
species,
carbonyl‐directed
hydrometalation
as
key
regioselective
control.
catalytic
method
provides
general
solution
hydrofunctionalization
alkynes
represents
efficient
pattern
assembling
highly
strained
enantioenriched
bioisosteres.
gem-Difluorinated
carbocyclic
rings
are
attractive
motifs
in
drug
development.
Herein,
we
report
the
transition-metal
free
cascade
reaction
of
bicyclo[1.1.0]butanes
(BCBs)
with
gem-difluorocyclopropenes
for
synthesis
gem-difluorinated
excellent
regio-
and
diastereoselectivity.
This
method
was
successfully
applied
to
provide
a
broad
range
cyclopentenes
cyclopropanes,
which
could
undergo
variety
difluoromethylene
(CF2)
retaining
transformations.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(7)
Опубликована: Дек. 21, 2022
Cyclobutenones
provide
a
straightforward
four-carbon
ring
platform
for
further
structural
elaborations
in
that
every
carbon
atom
of
the
could
be
potentially
functionalized.
We
report
here
nickel
catalyzed
enantioconvergent
Negishi
coupling
4-iodocyclobutenones
with
an
array
aryl
or
alkenyl
zinc
reagents
to
access
enantioenriched
4-substituted
cyclobutenones,
from
which
modular
approach
synthesis
1,2,3,4-tetrasubstituted
cyclobutanes
was
demonstrated.
Chemical Science,
Год журнала:
2023,
Номер
14(29), С. 7897 - 7904
Опубликована: Янв. 1, 2023
We
developed
a
copper-catalyzed
stereoselective
strategy
for
the
unified
synthesis
of
borylated
methylenecyclobutanes.
The
versatile
boromethylene
unit
greatly
expands
their
structural
diversity
and
potential
in
future
drug
discovery.
Abstract
Cyclobutene
scaffolds
occur
in
natural
products
and
bioactive
compounds.
Their
unique
structural
features
intrinsic
ring
strain
make
cyclobutene
a
type
of
important
building
block
synthetic
chemistry.
In
recent
years,
considerable
efforts
have
been
dedicated
to
the
synthesis
chiral
cyclobutenes.
Enantioselective
[2+2]
cycloadditions
functionalization
derivatives
emerged
as
powerful
reliable
protocols
for
achieving
this
goal,
resulting
significant
progress
field.
This
review
provides
comprehensive
summary
advancements
asymmetric
cyclobutenes,
discussion
is
logically
divided
into
four
parts
according
reaction
mode.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 12, 2024
Abstract
Enantioselective
synthesis
of
(spiro)cyclobutane
derivatives
poses
significant
challenges
yet
holds
promising
applications
for
both
synthetic
and
medicinal
chemistry.
We
report
here
a
nickel‐catalyzed
asymmetric
syn
‐hydrometalative
4‐
exo
‐
trig
cyclization
1,4‐alkynones
to
synthesize
alkenyl
cyclobutanols
with
tetrasubstituted
stereocenter.
This
strategy
features
broad
substrate
scope,
delivering
variety
trifluoromethyl‐containing
rigid
(spiro)carbocycle
skeletons
in
good
yields
high
enantioselectivities
(up
84
%
yield
98.5
:
1.5
er).
The
utility
is
demonstrated
through
stereospecific
transformations
into
fused
spiro
molecules.
Experimental
computational
mechanistic
studies
indicate
that
the
reaction
initiated
by
an
active
Ni−H
species,
carbonyl‐directed
hydrometalation
as
key
regioselective
control.
catalytic
method
provides
general
solution
hydrofunctionalization
alkynes
represents
efficient
pattern
assembling
highly
strained
enantioenriched
bioisosteres.
