Abstract
A
formal
[4+3]
cycloaddition
of
2‐alkylidenetrimethylene
carbonates
with
quinazoline‐derived
azomethine
imines
is
described.
Under
Pd
catalysis,
the
reaction
works
efficiently
under
room
temperature
to
afford
angular
quinazoline‐fused
seven‐membered
N,N,O
‐heterocycles.
variety
cyclic
and
were
well
tolerated
mild
conditions.
This
work
demonstrates
synthetic
utility
decarboxylative
cycloadditions
for
synthesis
polycyclic
aromatic
molecules.
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.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(42), С. 8593 - 8602
Опубликована: Янв. 1, 2023
A
palladium-catalyzed
decarboxylative
α-allylation
of
thiazolidinones
and
azlactones
with
aza-π-allylpalladium
zwitterionic
intermediates,
in
situ
generated
from
sulfonamido-substituted
allylic
carbonates,
is
successfully
developed.
This
method
allows
the
formation
a
series
structurally
diverse
5-alkylated
2-piperidones
under
mild
conditions
moderate
to
high
yields
(up
99%
yield).
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2864 - 2869
Опубликована: Янв. 1, 2024
A
novel
palladium-catalyzed
[4
+
4]
cycloaddition
of
2-pyrones
with
2-alkylidenetrimethylene
carbonates
has
been
developed
for
the
synthesis
bridged
eight-membered
oxygen
heterocycles
in
good
yields
and
excellent
stereoselectivities.
Organic Letters,
Год журнала:
2024,
Номер
26(41), С. 8945 - 8950
Опубликована: Окт. 9, 2024
A
novel
three-component
[4
+
3]
annulation
reaction
of
isatin-derived
azomethine
ylides
with
azadienes
was
developed
for
the
first
time
to
efficiently
synthesize
spirooxindole-diazepines
incorporating
a
benzothiophene
moiety
under
catalyst-free
conditions.
Effects
heteroatom
azadiene
on
chemoselectivity
investigated.
With
use
bearing
benzofuran
as
substrate,
dominant
pathway
changed
an
α-[3
2]
annulation.
When
indenone
used,
distinct
γ-[3
observed.
Density
functional
theory
calculations
revealed
that
delicate
balance
between
kinetic
accessibility
and
thermodynamic
driving
force
controlled
competition
different
reactions.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(48), С. 9507 - 9518
Опубликована: Янв. 1, 2023
This
review
summarizes
Pd-catalyzed
oxa-[4
+
n
]
dipolar
cycloadditions
of
1,4-O/C
dipoles
with
diverse
dipolarophiles,
affording
five-
to
nine-membered
O-heterocycles.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(4), С. 2364 - 2374
Опубликована: Фев. 7, 2024
Potassium
carbonate-catalyzed
(3
+
2)
cycloaddition
reaction
between
N-2,2,2-trifluoroethylisatin
ketimines
and
azodicarboxylates
has
been
developed,
constructing
a
series
of
novel
N-heterocycle
infused
spirooxindoles
in
good
to
excellent
yields
(up
98%)
under
milder
conditions.
The
presence
both
biologically
active
oxindole
trifluoromethyl-1,2,4-triazoline
moieties
these
spirocyclic
compounds
would
provide
new
lead
structures
the
discovery
heterocyclic
with
potential
pharmaceutical
activities.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 16, 2024
Comprehensive
Summary
We
report
a
palladium‐catalyzed
asymmetric
[4+4]
cycloaddition
reaction
between
2‐alkylidenetrimethylene
carbonate
and
electron‐deficient
indole‐2,3‐quinodimethanes
(
IQDMs
).
This
features
exclusive
regioselectivity,
high
yield
(up
to
98%),
excellent
enantioselectivity
95%
ee),
easy
scale‐up
without
any
loss
of
efficiency,
making
it
valuable
for
the
synthesis
indole‐fused
eight‐membered
oxa‐rings.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8363 - 8375
Опубликована: Июнь 7, 2024
Palladium-catalyzed
decarboxylation
of
5-methylene-1,3-oxazinan-2-ones
and
5-methylene-1,3-dioxan-2-ones
to
generate
aza-π-allylpalladium
oxa-π-allylpalladium
1,4-dipoles
for
[4
+
2]
cycloaddition
reaction
with
1,3,5-triazinanes
was
developed,
affording
a
wide
range
hexahydropyrimidine
1,3-oxazinane
derivatives
in
good
excellent
yields
(up
99%).
The
acyclic
sulfonamido-substituted
allylic
carbonates
as
1,4-dipole
precursors
also
apply
the
developed
synthesized
strategy,
achieving
synthesis
hexahydropyrimidines.
Moreover,
situ-generated
undergoing
dimeric
4]
were
demonstrated
by
construction
1,5-diazocane
derivatives.
