Molecules,
Год журнала:
2024,
Номер
30(1), С. 103 - 103
Опубликована: Дек. 30, 2024
Zwitterionic
π-allenyl
palladium
species
are
newly
developed
intermediates.
A
substrate-controlled
step
existed
in
the
cycloaddition
of
zwitterionic
with
tropsulfimides
or
tropones.
With
assistance
previously
experimental
studies,
allenyl/propargyl
was
provenly
found
by
HRMS.
Further
DFT
calculation
studies
show
that
generated
through
oxidative
addition
Pd(0),
which
can
be
promoted
Lewis
acid
like
Yb(OTf)3,
and
more
likely
undergoes
an
outer
sphere
nucleophilic
attack.
The
isomerization
is
caused
difference
dissociation
energy
between
intermediation
tropones,
forming
specificity.
ACS Catalysis,
Год журнала:
2024,
Номер
14(20), С. 15743 - 15750
Опубликована: Окт. 9, 2024
Medium-sized
rings
are
important
structural
units
in
organic
molecules
of
significant
interest.
However,
their
efficient
synthesis,
especially
a
highly
enantioselective
manner,
has
been
formidable
challenge.
Herein,
we
report
an
synthesis
medium-sized
aza-rings
by
Z-retentive
asymmetric
allylic
substitution-enabled
intermolecular
cascade
cyclization
via
iridium/cinchona
dual
catalysis.
The
reaction
was
performed
under
mild
conditions
and
with
good
functional
group
tolerance.
Various
nine-
to
eleven-membered
can
be
afforded
moderate
high
yields
(up
98%)
enantioselectivities
93%
ee).
utilization
both
Z-linear
dipole
precursor
binary
catalyst
is
critical
for
the
desired
reactivity.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(18), С. 4698 - 4702
Опубликована: Янв. 1, 2023
A
novel
asymmetric
[4
+
4]
dipolar
cycloaddition
of
aliphatic
1,4-dipoles
with
azadienes
was
developed
to
construct
chiral
benzofuran-
and
indene-fused
eight-membered
N-heterocycles
in
good
yields
excellent
stereoselectivities.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(40)
Опубликована: Май 31, 2024
Abstract
Bridged
cyclobutanes
and
sulfur
heterocycles
are
currently
under
intense
investigation
as
building
blocks
for
pharmaceutical
drug
design.
Two
formal
cycloaddition
modes
involving
bicyclobutanes
(BCBs)
pyridinium
1,4‐zwitterionic
thiolate
derivatives
were
described
to
rapidly
expand
the
chemical
space
of
sulfur‐containing
bridged
cyclobutanes.
By
using
Ni(ClO
4
)
2
catalyst,
an
uncommon
higher‐order
(5+3)
BCBs
with
quinolinium
was
achieved
broad
substrate
scope
mild
reaction
conditions.
Furthermore,
first
Lewis
acid‐catalyzed
asymmetric
polar
BCB
pyridazinium
accomplished.
In
contrast,
thiolates
undergo
Sc(OTf)
3
‐catalyzed
(3+3)
generate
thia‐norpinene
products,
which
represent
initial
instance
synthesizing
2‐thiabicyclo[3.1.1]heptanes
(thia‐BCHeps)
from
BCBs.
Moreover,
we
have
successfully
used
this
protocol
prepare
thia‐BCHeps‐substituted
analogues
bioactive
molecule
Pitofenone.
Density
functional
theory
(DFT)
computations
imply
that
kinetic
factors
govern
between
thiolate,
whereas
is
thermodynamic
control.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 17, 2025
Compared
to
smaller
or
larger
rings,
seven-
and
eight-membered
carbo-
heterocycles
are
typically
nonplanar
exhibit
greater
conformational
rigidity.
This
property
alone
can
impart
chirality
certain
7-
8-membered
ring
systems.
Herein,
we
summarize
recent
achievements
in
the
enantioselective
synthesis
of
this
class
inherently
chiral
medium
including
both
construction
modification,
as
well
applications
ligands
catalysts
derived
from
these
rigid
cyclic
scaffolds
asymmetric
catalysis.
Herein,
we
report
a
novel
ligand-switchable
Pd-catalyzed
carbene
coupling
reaction
employing
vinylethylene
carbonates
and
sulfoxonium
ylides.
By
proper
choice
of
ligands,
the
chemoselectivity
process
could
be
efficiently
regulated,
allowing
for
availability
dihydrofuran
or
dienol
scaffolds.
This
method
features
mild
conditions,
broad
scope,
remarkable
synthetic
utility.
Compound
6f
can
effectively
stimulate
secretion
GLP-1,
providing
promising
insight
into
development
small-molecule
agonists
GLP-1
receptor.
Considerable
progress
has
been
made
over
decades
in
synthetic
organic
chemistry
order
to
build
up
molecular
complexity,
often
through
the
design
of
advanced
catalytic
systems.
Yet,
simply
exposing
molecules
benchmark
oxidants
catalyst
free
conditions
can
sometimes
lead
surprising
and
highly
valuable
products.
Thus,
a
method
for
accessing
rare
9-membered
ketolactams
is
herein
described,
under
mild
oxidative
conditions.
Key
18O
17O
label
experiments
revealed
an
unexpected
oxygen
atom
migration
event
ring
expansion
process.
The
scope,
mechanism,
applications,
9
7
membered
contraction
opportunities
are
discussed.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(16), С. 4122 - 4130
Опубликована: Янв. 1, 2023
The
pyrazolo-azepino-centred
polyheterocyclic
fused
system
is
a
privileged
scaffold,
but
it
lacks
an
effective
synthetic
approach,
with
modular
synthesis
being
even
more
scarce.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(15), С. 3068 - 3072
Опубликована: Янв. 1, 2024
Allylphosphine
oxide
compounds
are
important
building
blocks
with
broad
applications
in
organic
synthesis
and
pharmaceutical
science.
Herein,
we
report
an
unprecedented
palladium-catalyzed
allylation
of
phosphine
oxides
vinylethylene
carbonates,
producing
various
phosphorus
allyl
alcohols
excellent
yields
high
