Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6637 - 6641
Опубликована: Июль 25, 2024
Starting
with
chiral
vinyl
sulfoxides
and
allenyl
ketones
or
allenoates,
a
triflic
acid-catalyzed
asymmetric
[3,3]-sigmatropic
rearrangement
of
sulfoniums
is
reported
to
have
direct
access
highly
functionalized
C4-chiral
cyclopentenones
(19
examples,
up
85%
yield
>95%
enantiomeric
excesses).
In
addition
the
use
these
compounds
as
key
building
blocks
in
organic
synthesis,
antiproliferative
activities
sulfoxide
substrates
corresponding
were
evaluated,
promising
cytotoxicity
against
HL-60
human
tumor
cell
line
was
found.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(43)
Опубликована: Авг. 17, 2022
Carbonyl
ylides
have
proven
to
be
powerful
synthons
for
the
efficient
construction
of
various
valuable
O-heterocycles,
and
formation
carbonyl
by
reaction
metal
carbenes
with
carbonyls
has
attracted
increasing
attention
over
past
decades.
However,
a
catalyst-controlled
highly
enantioselective
from
is
extremely
challenging.
Herein,
we
report
novel
copper-catalyzed
asymmetric
formal
[2+1]
[4+1]
annulations
diynes
ketones
via
ylides.
Importantly,
this
protocol
not
only
represents
first
example
successful
epoxidation
ylides,
but
also
constitutes
vinyl
cations
compounds.
This
method
leads
divergent,
practical
atom-economical
synthesis
range
chiral
oxiranes
dihydrofurans
in
moderate
excellent
yields
generally
enantioselectivities
diastereoselectivities
remote-stereocontrol
strategy.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Март 30, 2023
Axially
chiral
biaryls
widely
exist
in
natural
products
and
pharmaceuticals
are
used
as
ligands
catalysts
asymmetric
synthesis.
Compared
to
the
well-established
axially
6-membered
biaryl
skeletons,
examples
of
5-membered
have
been
quite
scarce,
mono-substituted
3-arylpyrrole
atropisomers
not
reported.
Here,
we
disclose
a
copper-catalyzed
atroposelective
diyne
cyclization
for
construction
range
arylpyrrole
good
excellent
yields
with
generally
enantioselectivities
via
oxidation
X-H
insertion
vinyl
cations.
Importantly,
this
protocol
only
represents
first
synthesis
atropisomers,
but
also
constitutes
example
atropisomer
Theoretical
calculations
further
support
mechanism
cation-involved
elucidate
origin
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(10)
Опубликована: Янв. 14, 2023
[2,3]-Sigmatropic
rearrangement
reaction
involving
sulfonium
ylide
(Doyle-Kirmse
reaction)
generated
from
metal
carbenes
represents
one
of
the
powerful
methods
for
construction
C(sp3
)-S
and
C-C
bonds.
Although
significant
advances
have
been
achieved,
asymmetric
versions
via
generation
ylides
rarely
reported
to
date,
they
so
far
limited
diazo
compounds
as
carbene
precursors.
Here,
we
describe
a
copper-catalyzed
enantioselective
Doyle-Kirmse
azide-ynamide
cyclization,
leading
practical
divergent
assembly
an
array
chiral
[1,4]thiazino[3,2-b]indoles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
excellent
yields
enantioselectivities.
Importantly,
this
protocol
unique
catalytic
non-diazo
approach
unprecedented
[2,3]-sigmatropic
α-imino
carbenes.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Recent
sulfinate
esters
chemistry
is
summarized
in
this
feature
article.
Efficient
methods
to
synthesize
diverse
from
readily
available
starting
materials
and
various
modern
transformations
of
are
introduced.
In
the
past
two
decades,
substantial
advances
have
been
made
on
asymmetric
alkyne
functionalization
by
activation
of
inert
alkynes.
However,
these
transformations
so
far
mostly
limited
to
transition
metal
catalysis,
and
chiral
Brønsted
acid-catalyzed
examples
are
rarely
explored.
Here,
we
report
a
dearomatization
reaction
phenol-
indole-tethered
homopropargyl
amines,
allowing
practical
atom-economical
synthesis
diverse
array
valuable
fused
polycyclic
enones
indolines
bearing
quaternary
carbon
stereocenter
contiguous
stereogenic
centers
in
moderate
good
yields
with
excellent
diastereoselectivities
generally
enantioselectivities
(up
>99%
enantiomeric
excess).
This
protocol
demonstrates
dearomatizations
via
vinylidene-quinone
methides.
Chemical Science,
Год журнала:
2023,
Номер
14(13), С. 3493 - 3500
Опубликована: Янв. 1, 2023
A
copper-catalyzed
asymmetric
cascade
cyclization
via
C(sp
2
)–O
bond
cleavage
is
disclosed,
affording
a
range
of
chromeno[3,4-
c
]pyrroles
bearing
triaryl
oxa-quaternary
carbon
stereocenter
in
high
yields
and
enantioselectivities.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(24)
Опубликована: Апрель 8, 2024
We
here
reported
a
highly
stereoselective
method
for
the
synthesis
of
polysubstituted
conjugated
dienes
from
α-aryl
α-diazo
alkynyl
ketones
and
pyrazole-substituted
unsymmetric
aminals
under
mild
conditions,
which
was
promoted
by
photo-irridation
involved
with
1,6-dipolar
intermediate
quadruple
sigmatropic
rearrangements,
successfully
developed.
In
this
transformation,
cleavage
four
bonds
recombination
five
were
implemented
in
one
operational
step.
This
protocol
provided
modular
tool
constructing
amines,
pyrazoles
α-alkynyl-α-diazoketones
one-pot
manner.
The
results
mechanistic
investigation
indicated
that
plausible
reaction
path
underwent
1,6-sigmatropic
rearrangement
instead
1,5-sigmatropic
rearrangement.
Acta Chimica Sinica,
Год журнала:
2023,
Номер
81(7), С. 793 - 793
Опубликована: Янв. 1, 2023
o-Hydroxyphenyl
substituted
p-quinone
methides
(p-QMs)
belong
to
a
class
of
p-QMs
with
unique
advantages.They
not
only
maintain
the
high
reactivity
p-QMs,
but
also
have
more
reactive
and
activation
sites
owing
introduction
hydroxyl
group.Therefore,
o-hydroxyphenyl
wide
applications
in
synthetic
medicinal
chemistry.The
catalytic
asymmetric
1,6-conjugate
addition
[4＋n]
cycloaddition
developed
very
rapidly
recent
years,
which
become
efficient
strategies
for
synthesis
chiral
oxygen-containing
heterocycles
arylmethanes
potential
bioactivity.This
review
summarizes
reactions
involving
points
out
remaining
challenges
this
research
area,
will
open
new
window
design
type
their
involved
reactions.
