Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 25, 2025
The
alkylation
of
nitro
compounds
is
an
efficient
technique
to
augment
molecular
complexity,
as
exemplified
by
the
Henry
reaction
and
Michael
addition
involving
sp2-hybridized
carbon.
However,
a
challenge
arises
in
with
sp3-hybridized
carbon
due
competing
nonproductive
O-alkylation.
In
this
study,
we
have
developed
manganese-promoted
oxidative
nitroalkanes
using
cyclopropyl
alcohols
via
solvent-caged
free-radical
nucleophilic
substitution
pathway.
This
process
yields
variety
γ-nitroketones,
including
sterically
hindered
tertiary
nitroalkanes,
thereby
introducing
novel
approach
for
C-alkylation
nitroalkanes.
Subsequent
reduction
facilitates
synthesis
pyrroline
pyrrolidine
derivatives.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(19), P. 7608 - 7612
Published: Sept. 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,
Journal Year:
2022,
Volume and Issue:
13(9), P. 2692 - 2700
Published: Jan. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(33)
Published: May 31, 2024
Abstract
gem
‐Diborylalkanes
are
highly
valuable
building
blocks
in
organic
synthesis
and
pharmaceutical
chemistry
due
to
their
ability
participate
multi‐step
cross‐coupling
transformations,
allowing
for
the
rapid
generation
of
molecular
complexity.
While
progress
has
been
made
synthetic
metholodology,
construction
β‐tertiary
C(sp
3
)‐rich
‐diborylalkanes
remains
a
challenge
substrate
limitations
steric
hindrance
issues.
An
approach
is
presented
that
utilizes
synergistic
photoredox
copper
catalysis
achieve
efficient
)−C(sp
)
alkyl
N
‐hydroxyphthalimide
esters,
which
can
easily
be
obtained
from
carboxylic
acids,
with
diborylmethyl
species,
providing
series
1°,
2°,
even
3°
β
positions.
Furthermore,
this
also
applied
complex
medicinal
compounds
natural
products,
offering
access
complexity
late‐stage
functionalization
drug
candidates.
Mechanistic
experiments
revealed
Cu(I)
species
participated
both
process
key
bond‐forming
step.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(18), P. 7219 - 7224
Published: Sept. 4, 2020
A
photocatalytic
synthesis
of
1,5-diaryl
pyrazoles
from
arenediazoniums
and
arylcyclopropanols
is
reported.
The
reaction
proceeded
under
mild
conditions
(rt,
20
min)
with
catalytic
[Ru(bpy)3]2+
blue-light
irradiation
exhibited
compatibility
several
functional
groups
(e.g.,
I,
SF5,
SO2NH2,
N3,
CN)
perfect
levels
regiocontrol.
Mechanistic
studies
(luminescence
spectroscopy,
CV,
DFT,
radical
trapping,
quantum
yield
determination)
documented
an
initial
oxidative
quenching
the
excited
photocatalyst
operation
a
radical-chain
mechanism.
The Journal of Organic Chemistry,
Journal Year:
2020,
Volume and Issue:
85(11), P. 7515 - 7525
Published: April 29, 2020
A
nickel-catalyzed
Suzuki
alkyl-aryl
coupling
of
cycloalkyl
silyl
peroxides
with
boronic
acids
is
reported.
The
primary
and
secondary
ketoalkyl
electrophiles
generated
through
C–C
bond
cleavage
were
amenable,
providing
rapid
access
to
a
variety
distal
arylated
alkyl
ketones.
radical
pathway
proposed
for
this
reaction.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(12), P. 1506 - 1509
Published: Jan. 1, 2021
Silver-catalyzed
direct
C–H
functionalization
of
cyclic
aldimines
with
cyclopropanols
and
cyclobutanols
via
a
radical-mediated
C–C
bond
cleavage
strategy
has
been
realized,
generating
the
desired
products
in
decent
yields
wide
substrate
scope.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(18)
Published: March 9, 2023
Organic
nitrates
are
broadly
applied
as
pharmaceuticals
(acting
efficient
nitric
oxide
donor),
energetic
materials,
building
blocks
in
organic
synthesis,
etc.
However,
practical
and
direct
methods
to
access
efficiently
still
rare,
mainly
due
the
lack
of
powerful
nitrooxylating
reagents.
Herein,
we
report
bench-stable
highly
reactive
noncyclic
hypervalent
iodine
reagents,
oxybis(aryl-λ3
-iodanediyl)
dinitrates
(OAIDNs,
2),
which
prepared
just
by
using
aryliodine
diacetate
HNO3
.
The
reagents
used
achieve
a
mild
operationally
simple
protocol
diverse
nitrates.
By
employing
2,
zinc-catalyzed
regioselective
nitrooxylation
cyclopropyl
silyl
ethers
is
realized
corresponding
β-nitrooxy
ketones
with
high
functional-group
tolerance.
Moreover,
series
catalyst-free
nitrooxylations
enolizable
C-H
bonds
carried
out
smoothly
afford
desired
within
minutes
mixing
substrates
2
dichloromethane.
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.
Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: Nov. 6, 2020
Abstract
The
catalytic
generation
of
homoenolates
and
their
higher
homologues
has
been
a
long-standing
challenge.
Like
the
transition
metal
enolates,
which
have
used
to
great
affect
in
synthesis
medicinal
chemistries,
much
potential,
albeit
largely
unrealized.
Herein,
nickel-catalyzed
homoenolates,
homologues,
via
decarbonylation
readily
available
cyclic
anhydrides
developed.
utility
nickel-bound
is
demonstrated
by
cross-coupling
with
unactivated
alkyl
bromides,
generating
diverse
array
aliphatic
acids.
A
broad
range
functional
groups
tolerated.
Preliminary
mechanistic
studies
demonstrate
that:
(1)
oxidative
addition
catalyst
faster
than
bromides;
(2)
nickel
bound
metallocycles
are
involved
this
transformation
(3)
undergoes
single
electron
transfer
(SET)
process
bromide.
