ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 255 - 264
Опубликована: Дек. 16, 2024
The
catalytic
asymmetric
synthesis
of
functionalized
C2-quaternary
indoline
scaffolds
has
garnered
significant
attention
in
organic
and
drug
discovery
due
to
the
inherent
challenges
potential
applications.
Herein,
we
present
a
facile
approach
utilizing
Pd-catalyzed
intramolecular
decarboxylative
amination
vinyl
benzoxazepinones,
leading
efficient
construction
challenging
chiral
2-vinyl-2-aryl/alkyl
frameworks
good
yields
with
high
enantioselectivities
(>50
examples,
up
83%
yield
97%
ee).
Furthermore,
these
indolines
can
be
readily
scaled
further
modified
access
complex
polycyclic
structures.
We
also
synthesized
several
indoline-based
ligands
that
exhibit
promising
efficiency
as
catalysts
reactions.
Computational
studies
provided
insight
into
inner-sphere
mechanism.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 19621 - 19628
Опубликована: Май 13, 2024
For
nearly
60
years,
significant
research
efforts
have
been
focused
on
developing
strategies
for
the
cycloaddition
of
bicyclobutanes
(BCBs).
However,
higher-order
and
catalytic
asymmetric
BCBs
long-standing
formidable
challenges.
Here,
we
report
Pd-catalyzed
ligand-controlled,
tunable
cycloadditions
divergent
synthesis
bridged
bicyclic
frameworks.
The
dppb
ligand
facilitates
formal
(5+3)
vinyl
oxiranes,
yielding
valuable
eight-membered
ethers
with
scaffolds
in
100%
regioselectivity.
Cy-DPEphos
promotes
selective
hetero-[2σ+2σ]
to
access
pharmacologically
important
2-oxabicyclo[3.1.1]heptane
(O-BCHeps).
Furthermore,
corresponding
O-BCHeps
94–99%
ee
has
achieved
using
chiral
(S)-DTBM-Segphos,
representing
first
cross-dimerization
two
strained
rings.
obtained
are
promising
bioisosteres
ortho-substituted
benzenes.
Abstract
The
synthesis
of
bicyclo[3.1.1]heptane
(BCHeps)
derivatives,
which
serve
as
three-dimensional
(3D)
bioisosteres
benzenes
and
are
the
core
skeleton
several
terpene
natural
products,
is
garnering
growing
interest.
(3+3)
cycloadditions
bicyclobutanes
(BCBs)
represent
an
attractive
method
for
efficiently
accessing
(hetero)BCHep
skeletons
with
100%
atom
economy.
Herein,
we
give
a
brief
summary
recent
achievements
in
this
approach
diverse
BCHep
emphasizing
our
progress
initial
palladium-catalyzed
vinyl
oxiranes.
1
Introduction
2
Radical
Cycloaddition
Reaction
3
Polar
4
Palladium-Catalyzed
Enantioselective
5
Conclusion
Organic Letters,
Год журнала:
2024,
Номер
26(20), С. 4262 - 4267
Опубликована: Май 9, 2024
A
novel
Pd-catalyzed
three-component
domino
reaction
for
the
stereoselective
synthesis
of
highly
functionalized
allyl
cinnamates
has
been
developed.
In
this
protocol,
a
sequential
process
C–C
bond
activation
and
intermolecular
allylic
substitution
was
well-organized.
The
key
transformation
is
in
situ
generated
hydrolysis
product
cyclopropenone,
which
triggered
new
with
vinylethylene
carbonates.
mechanism
investigated,
demonstrating
high
stereoselectivity
excellent
atomic
economy
process.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 5, 2025
Converting
carbon
dioxide
(CO2)
into
valuable
heterocycles
is
of
great
synthetic
value
but
usually
limited
to
five-
and
six-membered
ring
compounds.
Here,
we
report
a
catalytic
approach
for
transforming
this
renewable
seven-membered
using
double-stage
approach,
combining
silver-catalyzed
alkyne/CO2
coupling
subsequent
base-catalyzed
ring-expansion.
This
methodology
avoids
the
formation
thermodynamically
more
stable,
smaller-ring
by-products
has
good
functional
group
tolerance.
The
application
these
larger-ring
cyclic
carbonates
further
demonstrated
by
showing
their
unique
ability
serve
as
synthons
preparation
bicyclic
oxazolidinone
pharmacores
through
an
intramolecular
domino
sequence
that
involves
transient
ketimine
group,
various
other
intermolecular
transformations.
results
described
herein
significantly
expand
on
use
CO2
cheap
versatile
feedstock
generating
elusive
pharmaceutically
relevant
authors
heterocycles,
expansion.
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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Май 2, 2025
The
insertion
of
either
C-H
bond
or
C-O
via
cleavage
has
proven
to
be
a
very
attractive
strategy
for
the
construction
C-C
and
bonds
in
organic
synthesis.
However,
such
divergent
catalytic
asymmetric
reactions
selective
formation
C(sp3)-H
formal
C(sp3)-O
products
from
same
precursors
are
rarely
explored.
Herein,
we
report
ligand-controlled
reaction
vinyl
cations
by
non-diazo
approach,
leading
practical
atom-economical
assembly
range
chiral
spiro
fused
polycyclic
pyrroles
generally
moderate
excellent
yields
with
chemo-
enantioselectivities.
Importantly,
this
protocol
not
only
represents
rare
example
successful
reaction,
but
also
constitutes
an
enantioselective
1,6-C-H
carbenoid
into
acetals
approach.
An
unprecedented
successive
radical-promoted
thiolative
annulation/Pd-catalyzed
C-H
amination
of
N-benzyl-N-cyanopropiolamides
to
access
pyrrolo[2,1-b]quinazolin-1(9H)-ones
in
a
one-pot
manner
is
described.
Moreover,
altering
the
step
with
oxidation
(reagent
switch)
offered
maleimides
from
same
set
readily
accessible
precursors.
Both
transformations
display
versatility
across
wide
range
substrates,
enabling
efficient
various
functionalized
quinazolin-1-ones
and
good
yields.
A
difluorocarbene-enabled
regioselective
C(sp3)-O
bond
cleavage
of
oxiranes
has
been
developed.
The
protocol
provides
an
efficient
and
practical
approach
to
cyclic
carbonates
under
mild
conditions.
Significantly,
the
generation
difluorocarbene
with
BrCF2CO2Et/H2O
serving
as
a
CO2
equivalent
metal-free
conditions
disclosed.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(16), С. 4464 - 4469
Опубликована: Янв. 1, 2024
A
visible-light-induced
oxytrifluoromethylation
reaction
of
carbamate-containing
alkenes
has
been
reported
for
the
synthesis
diverse
cyclic
carbonates
and
vicinal
diols
bearing
trifluoroethyl
substituted
quaternary
centers.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(19), С. 5443 - 5453
Опубликована: Янв. 1, 2024
A
concise
construction
of
spiro[indoline-3,2′-pyrrol]-2-one
skeletons
is
reported.
This
reaction
proceeded
through
a
palladium-catalyzed
decarboxylative
allylic
alkylation
followed
by
DBU-mediated
intramolecular
cyclization.
