ChemistrySelect,
Journal Year:
2023,
Volume and Issue:
8(32)
Published: Aug. 23, 2023
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.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(1), P. 227 - 263
Published: May 29, 2020
This
review
describes
the
development
of
enantioselective
methods
for
ring
opening
cyclopropanes.
Both
approaches
based
on
reaction
nonchiral
cyclopropanes
and
(dynamic)
kinetic
resolutions
asymmetric
transformations
chiral
substrates
are
presented.
The
is
organized
according
to
substrate
classes,
starting
by
more
mature
field
donor-acceptor
Emerging
acceptor-
or
donor-only
then
last
part
reactive
three-membered
rings
substituted
with
unsaturations
a
particular
focus
vinylcyclopropanes,
alkylidenecyclopropanes,
vinylidenecyclopropanes.
In
two
decades,
has
grown
from
proof
concept
stage
broad
range
accessing
enantioenriched
building
blocks,
further
extensive
developments
can
be
expected
in
future.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(1), P. 3 - 79
Published: Oct. 21, 2020
The
carbon–carbon
(C–C)
bond
cleavage
of
cyclopropanols
is
a
wide
area
research
with
much
current
activity.
This
review
highlights
new
developments
in
this
over
the
past
two
decades.
A
summary
made
three
main
reactivity
modes,
namely,
homoenolate
chemistry,
β-keto
radical
and
acid-catalyzed
ring-opening,
as
well
all
other
methods
for
C–C
functionalization
cyclopropanols,
including
base-mediated
metal-catalyzed
insertions
eliminations,
oxidative
fragmentation
using
hypervalent
iodine
reagents,
reactions
donor–acceptor
pericylic
reactions.
Emphasis
placed
on
synthetic
utility
related
derivatives,
which
have
emerged
unique
three-carbon
synthons.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(19), P. 7101 - 7166
Published: Jan. 1, 2020
An
important
strategy
for
the
efficient
generation
of
diversity
in
molecular
structures
is
utilization
common
starting
materials
chemodivergent
transformations.
The
most
studied
solutions
switching
chemoselectivity
rely
on
catalyst,
ligand,
additive,
solvent,
temperature,
time,
pressure,
pH
and
even
small
modifications
substrate.
In
this
review
article
several
processes
have
been
selected
such
as
inter-
intramolecular
cyclizations,
including
carba-,
oxa-,
thia-
oxazacyclizations
promoted
mainly
by
Brønsted
or
Lewis
acids,
transition
metals
organocatalysts,
well
radical
reactions.
Catalyst-controlled
intra-
intermolecular
cyclizations
are
described
to
give
five-
six-membered
rings.
Cycloaddition
reactions
involving
(2+2),
(3+2),
(3+3),
(4+1),
(4+2),
(5+2),
(6+2)
(7+2)
useful
synthesis
cyclic
systems
using
metal
catalysts
acid-controlled
processes.
Addition
carba-
heteronucleophiles
unsaturated
conjugated
substrates
can
different
adducts
via
catalyst-,
acid-
solvent-dependent
Carbonylation
amines
phenols
carried
out
ligand-controlled
metal-catalyzed
multicomponent
Ring-opening
from
cyclopropanols,
cyclopropenols
epoxides
aziridines
applied
acyclic
versus
products
under
catalyst-control
acids.
Chemodivergent
reduction
performed
dissolving
metals,
sodium
borohydride
hydrogen
transfer
conditions
solvent
control.
Oxidation
include
oxygen
control
dioxiranes,
palladium
catalyzed
cross-coupling
boronic
acids
aromatic
allenic
compounds.
Other
alkylations
allylations
catalysis,
dimerization
acetylenes,
bromination
benzylic
substrates,
A3-couplings
catalyst-
reaction
condition-dependent
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(5), P. 2694 - 2698
Published: Oct. 14, 2020
Abstract
Catalylic
diastereo‐
and
enantioselective
hydroalkylation
of
3,3‐disubstituted
cyclopropenes
with
Co‐homoenolate
generated
in
situ
from
ring‐opening
easily
accessible
cyclopropanols
promoted
by
a
chiral
phosphine–cobalt
complex
is
presented.
Such
process
represents
the
unprecedented
direct
introduction
wide
range
functionalized
alkyl
groups
without
need
pre‐formation
stoichiometric
amounts
organometallic
reagents
onto
cyclopropane
motif,
affording
multi‐substituted
cyclopropanes
up
to
99
%
yield
>95:5
dr
98:2
er.
Functionalization
products
delivered
enantioenriched
that
are
otherwise
difficult
access.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(5), P. 3013 - 3093
Published: Jan. 1, 2021
This
review
provides
an
overview
of
the
fundamental
concepts
and
recent
developments
in
a
wide
range
enantioselective
transformations
involving
oxa-
azabicyclic
alkenes.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(6), P. 2292 - 2297
Published: March 8, 2021
Ligand-controlled,
palladium-catalyzed
asymmetric
[4+4]
and
[2+4]
cycloaddition
reactions
of
benzofuran-derived
azadienes
have
been
developed.
Taking
advantage
chiral
P,N-ligand
(S,Rp)-PPFA,
we
obtained
a
variety
benzofuro[2,3-c][1,5]
oxazocines
in
good
yields
with
excellent
enantioselectivities
via
reactions.
Employing
P,P-ligand
(S)-Cl-MeO-BIPHEP,
the
chemo-
regioselectivities
were
switched
to
synthesize
tetrahydropyran-fused
spirocyclic
compounds
efficiency
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(6), P. 3588 - 3598
Published: Feb. 3, 2023
Catalytic
enantioselective
functionalization
of
cyclobutenes
constitutes
a
general
and
modular
strategy
for
construction
enantioenriched
complex
cyclobutanes
bearing
multiple
stereogenic
centers,
as
chiral
four-membered
rings
are
common
motifs
in
biologically
active
molecules
versatile
intermediates
organic
synthesis.
However,
synthesis
through
such
remained
significantly
limited.
Herein,
we
report
series
unprecedented
cobalt-catalyzed
carbon-carbon
bond
forming
reactions
that
initiated
carbometalation.
The
protocols
feature
diastereo-
introduction
allyl,
alkynyl,
functionalized
alkyl
groups.
Mechanistic
studies
indicated
an
unusual
1,3-cobalt
migration
subsequent
β-carbon
elimination
cascade
process
occurred
the
allyl
addition.
These
new
discoveries
established
elementary
cobalt
catalysis
extension
diversity
nucleophiles
transformations
cyclobutenes.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(21), P. 8805 - 8809
Published: Oct. 18, 2019
Metal
homoenolates
are
valuable
synthetic
intermediates
which
provide
access
to
β-functionalized
ketones.
In
this
report,
we
disclose
a
Ni-catalyzed
β-alkylation
reaction
of
cyclopropanol-derived
using
redox-active
N-hydroxyphthalimide
(NHPI)
esters
as
the
alkylating
reagents.
The
is
compatible
with
1°,
2°,
and
3°
NHPI
esters.
Mechanistic
studies
imply
radical
activation
ester
2e
β-carbon
elimination
occurring
on
cyclopropanol.
Bulletin of the Chemical Society of Japan,
Journal Year:
2020,
Volume and Issue:
94(1), P. 265 - 280
Published: Sept. 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.
