Organic Letters,
Год журнала:
2023,
Номер
25(12), С. 2030 - 2035
Опубликована: Март 20, 2023
Ten-membered
lactones
are
the
core
units
of
many
biologically
active
natural
products
but
with
a
great
synthetic
challenge.
Based
on
principle
vinylogy,
novel
types
cyclic
vinylogous
anhydrides
have
been
designed
as
five-carbon
carbonyl
synthons,
further
applied
in
[5
+
5]
annulation
vinylethylene
carbonates
under
chiral
palladium
catalysis.
This
strategy
features
excellent
regioselectivity,
mild
conditions,
and
broad
substrate
scope,
affording
range
spiro
ten-membered
bearing
oxindole
pyrrolidinone
motif
yield
(up
to
99%)
moderate
high
enantioselectivity
89%
ee).
Chemical Science,
Год журнала:
2023,
Номер
14(11), С. 3024 - 3029
Опубликована: Янв. 1, 2023
Inspired
by
a
fungicide,
we
designed
5-vinyloxazolidine-2,4-diones
as
new
precursors
of
π-allylpalladium
zwitterionic
intermediates
and
developed
palladium-catalyzed
asymmetric
(5
+
3)
cycloaddition
with
azomethine
imines
(3
2)
1,1-dicyanoalkenes.
Both
reactions
proceeded
smoothly
under
mild
reaction
conditions
to
produce
various
chiral
heterocyclic
compounds
in
high
yields
excellent
enantioselectivities.
These
results
revealed
that
were
type
suitable
precursor
for
palladium
catalysis
will
find
extensive
applications
Pd-catalyzed
such
allylic
alkylation.
Chemical Communications,
Год журнала:
2023,
Номер
59(49), С. 7483 - 7505
Опубликована: Янв. 1, 2023
Copper-catalyzed
decarboxylative
reactions
are
powerful
strategies
for
the
construction
of
widely
available
skeletons
such
as
allenes,
ethynyl-containing
heterocycles,
and
quaternary
carbon
centers.
Organic Letters,
Год журнала:
2024,
Номер
26(8), С. 1589 - 1594
Опубликована: Фев. 22, 2024
This
study
demonstrates
a
highly
efficient
regiodivergent
ligand-controlled
palladium-catalyzed
cycloaddition
reaction
of
vinyloxazolidine-2,4-diones
with
1,3,5-triazinanes.
In
the
presence
diphosphine
ligand,
proceeds
via
(5+2)
pathway
to
afford
1,3-diazepin-4-ones
in
excellent
yields,
while
using
monophosphine
smoothly
(3+2)
give
imidazolidin-4-ones
good
yields.
Organic Letters,
Год журнала:
2022,
Номер
24(45), С. 8348 - 8353
Опубликована: Ноя. 10, 2022
A
palladium-catalyzed
enantioselective
α-allylation
of
deconjugated
butenolides
with
aza-π-allylpalladium
1,4-diploes,
in
situ
generated
from
palladium-mediated
decarboxylation
cyclic
carbamates
and
amide-substituted
acyclic
carbonates,
has
been
successfully
developed.
An
array
enantioenriched
2-piperidones
bearing
an
all-carbon
quaternary
stereocenter
were
obtained
high
yields
excellent
enantioselectivities
(up
to
99%
yield
ee).
The
utility
this
method
was
also
showcased
by
a
large-scale
reaction
synthetic
transformations
the
product.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(19), С. 10491 - 10496
Опубликована: Май 4, 2023
Strained
cyclic
allenes
are
a
class
of
in
situ-generated
fleeting
intermediates
that,
despite
being
discovered
more
than
50
years
ago,
has
received
significantly
less
attention
from
the
synthetic
community
compared
to
related
strained
intermediates.
Examples
trapping
that
involve
transition
metal
catalysis
especially
rare.
We
report
first
annulations
highly
reactive
with
π-allylpalladium
species.
By
varying
ligand
employed,
either
two
isomeric
polycyclic
scaffolds
can
be
obtained
high
selectivity.
The
products
heterocyclic
and
sp3-rich
bear
or
three
new
stereocenters.
This
study
should
encourage
further
development
fragment
couplings
rely
on
for
rapid
assembly
complex
scaffolds.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3310 - 3315
Опубликована: Апрель 8, 2024
A
catalyst
system
consisting
of
a
chiral
phosphoramidite
ligand
and
Pd2(dba)3·CHCl3
causes
the
decarboxylation
5-vinyloxazolidine-2,4-diones
to
generate
amide-containing
aza-π-allylpalladium
1,3-dipole
intermediates,
which
are
capable
triggering
dearomatization
3-nitroindoles
for
diastereo-
enantioselective
[3+2]
cycloaddition,
leading
formation
series
highly
functionalized
pyrroloindolines
containing
three
contiguous
stereogenic
centers
with
excellent
results
(up
99%
yield,
88:12
dr,
96%
ee).
Abstract
Oxazocines
are
key
structural
intermediates
in
the
synthesis
of
natural
products
and
pharmaceutical
molecules.
However,
oxazocines
especially
a
highly
enantioselective
manner,
is
long‐standing
formidable
challenge
due
to
unfavorable
energetics
involved
cyclization.
Herein,
series
new
PNP‐Ligand
P
‐chiral
stereocenter
first
designed
synthesized,
called
MQ‐Phos
,
successfully
applied
it
Pd‐catalyzed
higher‐order
formal
[4+4]‐cycloaddition
α
β
‐unsaturated
imines
with
2‐(hydroxymethyl)‐1‐arylallyl
carbonates.
The
reaction
features
mild
conditions,
excellent
regio‐
enantiocontrol
broad
substrate
scope
(54
examples).
Various
medium‐sized
rings
can
be
afforded
moderate
yields
(up
92%)
enantioselectivity
99%
ee).
newly
developed
critical
for
ring
catalytic
reactivity
enantioselectivity.
