The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(7), С. 4508 - 4523
Опубликована: Март 15, 2022
The
scope
of
chemoselective
β-hydride
elimination
in
the
context
arylation/alkenylation
homoenolates
from
cyclopropanol
precursors
using
organoboronic
reagents
as
transmetalation
coupling
partners
was
examined.
reaction
optimization
paradigm
revealed
a
simple
ligand-free
Pd(II)
catalytic
system
to
be
most
efficient
under
open
air
conditions.
preparative
scope,
which
investigated
with
48
examples,
supported
applicability
this
wide
range
substrates
tolerating
variety
functional
groups
while
delivering
β-substituted
enone
and
dienone
derivatives
62-95%
yields.
Bulletin of the Chemical Society of Japan,
Год журнала:
2020,
Номер
94(1), С. 265 - 280
Опубликована: Сен. 28, 2020
Abstract
Metal
homoenolates
represent
uniquely
useful
organometallic
intermediates
in
synthetic
chemistry,
allowing
umpolung
synthesis
of
β-functionalized
carbonyl
compounds.
While
siloxycyclopropanes
had
been
established
as
reliable
precursors
to
homoenolates,
often
stoichiometric,
for
diverse
carbon–carbon
bond
forming
reactions,
unprotected
cyclopropanols
have
emerged
alternative
and
attractive
catalytically
generated,
carbon–heteroatom
bond-forming
reactions.
This
review
article
provides
an
overview
the
development
such
homoenolate
transformations,
classified
with
respect
metals
involved
cyclopropane
ring
opening.
Organic Letters,
Год журнала:
2021,
Номер
23(19), С. 7608 - 7612
Опубликована: Сен. 16, 2021
The
ring
opening
of
cyclopropanols
is
rarely
used
in
multicomponent
reactions.
Herein
we
report
the
three-component
reaction
with
alkenes
and
tert-butyl
hydroperoxide
(TBHP)
catalyzed
by
an
iron
catalyst.
This
protocol
enables
incorporation
both
β-carbonyl
fragment
a
peroxy
unit
across
C═C
double
bond
regioselectively,
thus
allowing
efficient,
facile
access
to
5-oxo
peroxides.
Modification
biologically
active
molecules
various
downstream
derivatizations
peroxides
are
also
demonstrated.
Chemical Science,
Год журнала:
2022,
Номер
13(9), С. 2692 - 2700
Опубликована: Янв. 1, 2022
Palladium-catalyzed
tandem
activation
and
functionalization
of
readily
accessible
cyclopropanols
have
been
demonstrated
to
access
valuable
conjugated
enynes
from
1,3-diynes
with
high
stereo-selectivity.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(13), С. 8722 - 8737
Опубликована: Июнь 14, 2023
A
phosphine-catalyzed
ring-opening
addition
reaction
of
cyclopropenones
with
a
variety
nucleophiles
(NuH),
including
oxygen-,
nitrogen-,
sulfur-,
and
carbon-based
ones,
has
been
investigated,
which
produces
potentially
useful
α,β-unsaturated
carbonyl
derivatives
in
high
yields
(up
to
99%),
regioselectivity,
exclusive
E-selectivity.
The
proceeds
efficiency
under
very
mild
conditions
using
only
1
mol
%
PPh3
as
the
catalyst
at
room
temperature.
method
is
also
amenable
for
synthesis
deuterated
alkenes
when
(NuD)
are
employed.
mechanism
investigated
by
experiments
DFT
calculations,
suggests
an
α-ketenyl
phosphorus
ylide
key
intermediate
catalytic
cycle
that
captures
stereoselective
manner.
Abstract
Cyclopropanols,
due
to
their
particular
chemistry,
can
participate
in
various
synthetic
reactions
with
retention
or
cleavage
of
the
strained
three‐membered
ring.
Direct
cross‐coupling
ring‐opening
reaction
such
molecules
access
organic
compounds,
as
ketones
has
great
importance
medicinal
chemistry
and
material
sciences.
Hence,
coupling
reaction/cyclization
cyclopropanols
for
constructing
new
valuable
presence
a
transition
metal
catalyst
under
metal‐free
conditions
is
described
this
context.
The
features
are
discussed,
mechanisms
challenging
highlighted.
The Journal of Organic Chemistry,
Год журнала:
2020,
Номер
86(1), С. 1074 - 1083
Опубликована: Дек. 22, 2020
A
redox
neutral
Co(III)-catalyzed
annulation
of
α,β-unsaturated
oxime
ether
with
alkyne
has
been
reported.
Multisubstituted
pyridines
were
synthesized
in
good
yields
without
the
use
any
heavy
metal
oxidants.
The
developed
methodology
tolerates
a
variety
functional
groups.
Notably,
this
transformation
applied
to
late-stage
modification
bioactive
molecule
dehydropregnenolone.
The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(3), С. 2682 - 2695
Опубликована: Янв. 11, 2021
Strain-driven
palladium/N-heterocyclic
carbene-catalyzed
C–C
bond
activation
of
diphenylcyclopropenone
(DPC)
has
been
explored
for
one-step
access
to
trisubstituted
α,β-unsaturated
esters
and
amides.
The
designed
transformation
works
under
mild
conditions
providing
exclusively
a
single
stereoisomer.
Mechanistic
studies
support
the
oxidative
addition
cyclopropenone
in-situ-generated
Pd(0)
intermediate.
We
have
proved
that
vinylic
hydrogen
in
product
is
coming
from
phenol/aniline
through
deuterium-labeling
studies.
Late-stage
functionalization
bioactive
molecules
such
as
procaine,
estrone,
hymecromone
demonstrates
robustness
this
protocol.
