Organic Letters,
Год журнала:
2023,
Номер
25(20), С. 3591 - 3595
Опубликована: Май 16, 2023
A
methodology
for
the
construction
of
sterically
congested
quaternary
centers
via
trapping
vinyl
carbocations
with
silyl
ketene
acetals
is
disclosed.
This
main
group-catalyzed
α-vinylation
reaction
advantageous
as
methods
to
access
these
motifs
are
limited.
Moreover,
β,γ-unsaturated
carbonyl
moieties
and
tetrasubstituted
alkenes
present
in
various
bioactive
natural
products
pharmaceuticals,
this
catalytic
platform
offers
a
means
accessing
them
using
simple
inexpensive
materials.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15036 - 15042
Опубликована: Июль 10, 2023
A
catalytic
protio-semipinacol
ring-expansion
reaction
has
been
developed
for
the
highly
enantioselective
conversion
of
tertiary
vinylic
cyclopropyl
alcohols
into
cyclobutanone
products
bearing
α-quaternary
stereogenic
centers.
The
method
relies
on
cocatalytic
effect
a
chiral
dual-hydrogen-bond
donor
(HBD)
with
hydrogen
chloride.
Experimental
evidence
is
provided
stepwise
mechanism
where
protonation
alkene
generates
short-lived,
high-energy
carbocation,
which
followed
by
C–C
bond
migration
to
deliver
enantioenriched
product.
This
research
applies
strong
acid/chiral
HBD
cocatalysis
weakly
basic
olefinic
substrates
and
lays
foundation
further
investigations
reactions
involving
cationic
intermediates.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 25, 2024
The
asymmetric
Büchner
reaction
and
related
arene
cyclopropanations
represent
one
type
of
the
powerful
methods
for
enantioselective
dearomatization.
However,
examples
reactions
via
a
non-diazo
approach
are
quite
scarce,
cyclopropanation
based
on
alkynes
has
not
been
reported.
Herein,
we
disclose
an
by
copper-catalyzed
controllable
cyclization
N-propargyl
ynamides
vinyl
cation
intermediates,
leading
to
chiral
tricycle-fused
cycloheptatrienes
benzonorcaradienes
in
high
yields
enantioselectivities.
Importantly,
this
protocol
represents
cations.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1000 - 1005
Опубликована: Янв. 31, 2024
Medium-sized
rings
(8–11-membered
cycles)
are
often
more
challenging
to
synthesize
than
smaller
(5–7-membered
due
ring
strain.
Herein,
we
report
a
catalytic
method
for
forming
8-
and
9-membered
that
proceeds
via
the
intramolecular
Friedel–Crafts
reactions
of
vinyl
carbocation
intermediates.
These
reactive
species
generated
catalytically
through
ionization
toluenesulfonates
by
Lewis
acidic
lithium
cation–weakly
coordinating
anion
salt.
The Chemical Record,
Год журнала:
2023,
Номер
23(12)
Опубликована: Окт. 11, 2023
Abstract
Five‐membered
carbocycles
are
ubiquitously
found
in
natural
products,
pharmaceuticals,
and
other
classes
of
organic
compounds.
Within
this
category,
cyclopentenes
deserve
special
attention
due
to
their
prevalence
as
targets
well
key
intermediates
for
synthesizing
more
complex
molecules.
Herein,
we
offer
an
overview
summarizing
some
significant
recent
advances
the
catalytic
assembly
structural
motif.
A
great
variety
synthetic
methodologies
strategies
covered,
including
transition
metal‐catalyzed
or
organocatalyzed
processes.
Both
inter‐
intramolecular
transformations
documented.
On
ground,
our
expertise
application
C−H
functionalization
reactions
oriented
towards
formation
ring
its
subsequent
selective
is
embedded.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(13)
Опубликована: Фев. 15, 2024
Abstract
Direct
C−H
functionalization
is
an
important
strategy
for
the
rapid
synthesis
of
valuable
organic
molecules.
Radical‐involved
remote
C(sp
3
)‐H
based
on
hydrogen
atom
transfer
(HAT)
becomes
method
enabling
selective
direct
transformation
bonds
at
specific
distal
position(s).
In
recent
years,
copper‐catalyzed
fluoroamide‐directed
bond
through
intramolecular
HAT
has
served
as
a
robust
and
elegant
assembly
variety
functionalized
(sulfon)amides
related
derivatives.
This
review
focuses
advances
in
this
area.
These
transformations
proceed
effectively
with
high
selectivities
good
functional
group
compatibility
under
mild
conditions.
Chemistry - A European Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
The
pentafluorosulfanyl
(SF5-)
group
has
been
the
subject
of
a
surge
interest
in
past
decade,
but
there
is
still
little
practicality
associated
with
its
synthesis
and
installation.
Herein
reported
first
continuous
flow
chloride
(SF5Cl),
most
common
reagent
for
SF5-substituted
compounds.
based
on
inexpensive
easy-to-handle
reagents:
sulfur
powder
(S8),
trichloroisocyanuric
acid
(TCCA)
potassium
fluoride
(KF).
To
this
end,
custom-made
stirring
reactor
was
designed
to
allow
fast,
safe,
highly
efficient
on-demand
SF5Cl.
resulting
SF5Cl
solution
showcased
radical
addition
alkynes
telescoped
fashion.
Spintronic
devices
are
emerging
as
an
approach
to
realize
performance
and
energy
efficiency
beyond
what
is
possible
with
traditional
electronic
devices.
State-of-the-art
metals
doped
conjugated
polymers
used
for
spin
manipulation
suffer
from
fundamental
stability
issues.
We
leveraged
stereoselective
cationic
polymerization
design
a
polymer
stable
persistent
radical
in
each
repeat
unit
that
enables
the
long-range
order
necessary
transport.
This
overcomes
conventional
requirements
doping
organic
spin-pumping
while
showcasing
high
conductivity,
long
spin-diffusion
lengths,
processability.
Molecular-level
alterations
stereochemistry
were
critical
controlling
spin-spin
interactions
alignment.
Stereoregular
neutral
radicals
represent
previously
unidentified
class
of
materials
manipulating
spins
over
distances
applications
next-generation
information
storage.
ACS Central Science,
Год журнала:
2025,
Номер
11(5), С. 805 - 815
Опубликована: Май 2, 2025
Significant
advancements
have
been
made
in
the
catalytic
asymmetric
dearomatization
of
indoles
for
constructing
valuable
chiral
polycyclic
N-heterocycles.
However,
dearomative
cyclopropanation
continues
to
pose
a
formidable
challenge.
Furthermore,
diverse
transformations
indoline-fused
cyclopropanes
via
strain
release
remain
largely
unexplored,
potentially
unveiling
new
chemistry.
Here,
we
disclose
Cu-catalyzed
indole-diynes
and
subsequent
[3
+
2]
cycloaddition
with
oxygen,
facilitating
divergent
atom-economical
synthesis
enantioenriched
cyclopropane-
1,2-dioxolane-fused
indolines
moderate
excellent
yields
generally
outstanding
diastereo-
enantioselectivities
broad
substrate
scope.
Importantly,
this
protocol
not
only
represents
first
utilizing
alkynes
as
carbene
precursors
but
also
constitutes
construction
1,2-dioxolanes
high
stereoselectivity.
Interestingly,
Brønsted
acid-promoted
ring-opening
rearrangement
cyclopropane-fused
display
distinctive
chemoselectivity
afford
cyclohepta-[b]-indoles
good
efficiency
enantiocontrol.
In
addition,
both
potential
reaction
pathways
origins
control
within
tandem
sequence
are
robustly
supported
by
experiments
theoretical
calculations.
