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 Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(19), P. 4941 - 4971
Published: Jan. 1, 2023
A
summary
of
the
various
ring
opening
reactions
strained
and
unstrained
cycloalkanols
is
elaborated
in
present
review.
Key
emphasis
on
reactivities
pertaining
to
cyclopropanols,
cyclobutanols
higher
analogues
provided.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(3), P. 1375 - 1380
Published: Jan. 1, 2024
A
visible-light-mediated
tandem
ring
opening/1,6-conjugate
addition
of
cyclobutanols
with
p
-quinone
methides
was
developed.
This
protocol
allowed
the
formation
δ,δ-diaryl
ketones
in
presence
a
readily
available
organic
photocatalyst.
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.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2058 - 2062
Published: March 17, 2023
A
Fe(NO3)3-mediated
ring-opening
arylation
of
cyclopropanol
with
the
electron-rich
pyrrole
has
been
developed,
which
might
proceed
through
oxidative
radical
ring
opening
followed
by
cyclization
to
motif
and
then
aromatization.
This
method
enables
direct
without
prefunctionalization
thus
allows
rapid
access
a
diverse
array
chiral
5,6,7,8-tetrahydroindolizines
from
easily
available
amino
acid
esters.
The
synthetic
utility
demonstrated
asymmetric
synthesis
alklaoids
(-)-indolizidine
167B,
(+)-indolizidine
209D,
(+)-monomorine
I,
natural
product
analogue.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 17, 2025
ConspectusThe
Mannich
reaction,
involving
the
nucleophilic
addition
of
an
enol(ate)
intermediate
to
imine
or
iminium
ion,
is
one
most
widely
used
synthetic
methods
for
synthesis
β-amino
carbonyl
compounds.
Nevertheless,
homo-Mannich
which
utilizes
a
homoenolate
as
partner
and
provides
straightforward
access
valuable
γ-amino
compounds,
remains
underexplored.
This
can
be
largely
attributed
difficulties
in
generation
manipulation
species,
despite
various
equivalents
that
have
been
developed.
Among
developed,
cyclopropanol
stands
out
due
its
intriguing
reactivities
endowed
by
highly
strained
cyclopropane.
Upon
activation
metal,
cyclopropyl
alcohol
prone
undergo
endocyclic
C(sp3)–C(sp3)
bond
cleavage
give
β-keto
radical
intermediate,
sets
stage
diverse
range
transformations.
account
outlines
our
recent
progress
development
reaction
applications
natural
product
total
synthesis.
new
methodology
classified
into
two
subtypes:
1)
with
imines
ions
2)
homo-Mannich-type
heteroarenes.
Through
different
ways
generate
ions,
tandem
sequential
reactions
C–H
oxidation/homo-Mannich,
Bischler–Napieralski/homo-Mannich,
asymmetric
allylation/homo-Mannich
leading
rapid
assembly
core
scaffolds
sarpagine,
koumine,
ibophyllidine,
Aspidosperma,
Melodinus,
Kopsia
alkaloids.
Besides
ring-opening
indole
pyrrole
rings
deliver
schizozygane
indolizidine
Based
on
these
advancements,
we
accomplished
29
alkaloids
belonging
8
families.
In
this
Account,
present
complete
picture
works
concerning
design,
method
development,
It
anticipated
methodologies
will
find
broad
realm
