Chemical Communications,
Год журнала:
2022,
Номер
58(46), С. 6646 - 6649
Опубликована: Янв. 1, 2022
In
this
paper,
a
new
type
of
δ-vinylvalerolactone
was
designed
and
synthesized,
used
as
precursor
in
Pd-catalyzed
[6+3]
cycloaddition
with
azomethine
imines,
leading
to
nine-membered
1,2-dinitrogen-containing
heterocycles
77-98%
yields
>20
:
1
d.r.
These
ring-fused
products
were
further
transformed
into
unusual
tetracyclic
bridged-ring
compounds
without
loss
the
diastereoselectivities.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(47), С. 24941 - 24949
Опубликована: Сен. 17, 2021
The
development
of
efficient
and
straightforward
methods
for
obtaining
all
optically
active
isomers
structurally
rigid
spirocycles
from
readily
available
starting
materials
is
great
value
in
drug
discovery
chiral
ligand
development.
However,
the
stereodivergent
synthesis
bearing
multiple
stereocenters
remains
an
unsolved
challenge
owing
to
steric
hindrance
ring
strain.
Herein,
we
report
enantio-
diastereodivergent
through
dual-metal-catalyzed
[3+2]
annulation
oxy
π-allyl
metallic
dipoles
with
less
commonly
employed
nucleophilic
(imino
esters).
A
series
spiro
compounds
a
pyrroline
olefin
were
easily
synthesized
manner
(up
19:1
dr,
>99
%
ee),
which
showed
promise
as
new
type
N-olefin
ligand.
Preliminary
mechanistic
studies
also
carried
out
understand
process
this
bimetallic
catalysis.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(13), С. 3475 - 3501
Опубликована: Янв. 1, 2021
Carbocyclic
and
heterocyclic
compounds
could
be
constructed
through
the
palladium-catalyzed
annulation
reactions
of
zwitterionic
π-allyl
palladium
or
propargyl
complexes
with
unsaturated
electrophiles.
Abstract
Palladium‐catalyzed
decarboxylative
cycloadditions
have
emerged
as
highly
effective
methods
for
constructing
structurally
diverse
carbo‐
and
heterocycles
because
of
the
formation
at
least
two
carbon‐carbon
or
carbon‐heteroatom
bonds
in
a
single
step.
It
is
great
interest
to
chemists
that
this
type
cycloaddition
reactions
possesses
some
special
advantages
such
high
reactivity,
exclusive
regioselectivity,
good
functional
group
compatibility.
Based
on
these
qualities,
palladium‐catalyzed
present
strong
ability
synthetic
chemistry
been
flourished
especially
last
five
years.
In
review,
achievements
involving
cyclic
carbonates,
carbamates,
lactones
accessing
oxacyclo‐,
azacyclo‐
carbocyclic
compounds
are
addressed.
Mechanistic
insights
applications
toward
synthesis
natural
products
discussed.
The
challenges
opportunities
field
also
outlined.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Авг. 12, 2022
Abstract
[3+2]
Cycloaddition
is
a
step-
and
atom-economic
method
for
the
synthesis
of
five-membered
rings.
Despite
great
success
1,3-dipolar
cycloadditions,
radical
annulation
alkynes
remains
formidable
challenge.
Herein,
photoinduced
decatungstate-catalyzed
cycloaddition
various
internal
using
abundant
aliphatic
aldehydes
as
three-carbon
synthon
developed,
producing
elaborate
cyclopentanones
in
100%
atom
economy
with
excellent
site-,
regio-,
diastereoselectivity
under
mild
conditions.
The
catalytic
cycle
consists
hydrogen
abstraction
from
aldehydes,
addition,
1,5-hydrogen
transfer,
anti-Baldwin
5-endo-trig
cyclization,
back
abstraction.
power
this
showcased
by
late-stage
elaboration
medicinally
relevant
molecules
total
or
formal
(±)-β-cuparenone,
(±)-laurokamurene
B,
(±)-cuparene.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(2), С. 883 - 971
Опубликована: Дек. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Янв. 29, 2024
Organic
molecules
bearing
chiral
sulfur
stereocenters
exert
a
great
impact
on
asymmetric
catalysis
and
synthesis,
drugs,
materials.
Compared
with
acyclic
ones,
the
catalytic
synthesis
of
thio-heterocycles
has
largely
lagged
behind
due
to
lack
efficient
synthetic
strategies.
Here
we
establish
first
modular
platform
access
thio-oxazolidinones
via
Pd-catalyzed
[3+2]
annulations
vinylethylene
carbonates
sulfinylanilines.
This
protocol
is
featured
by
readily
available
starting
materials,
high
enantio-
diastereoselectivity.
In
particular,
an
unusual
effect
non-chiral
supporting
ligand
diastereoselectivity
was
observed.
Possible
reaction
mechanisms
stereocontrol
models
were
proposed.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(9), С. 3595 - 3603
Опубликована: Фев. 25, 2021
For
nearly
30
years,
considerable
research
effort
has
been
focused
on
the
development
of
methods
for
catalytic
(3
+
2)
cycloaddition
reactions
palladium-oxyallyl
species
with
alkenes.
However,
because
C–O
bond
formation
is
kinetically
favored,
cycloadditions
achieved
to
date
have
involved
reductive
elimination.
We
herein
report
a
method
lithium
triflate-promoted
1,3-dienes
that
proceed
via
pathway
terminated
C–C
give
five-membered
carbocycle.
Coordination
ion
alkoxide
moiety
disrupts
elimination
and
forms
metal-enolate
tethered
π-allyl-Pd.
The
π-allyl-Pd
then
accepts
intramolecular
allylic
attack
from
enolate
form
carbocyclic
products.
Furthermore,
by
tuning
steric
properties
palladium
ligand,
we
could
also
accomplish
competing
(4
3)
cycloadditions,
thus
this
provides
regiodivergent
access
both
cyclopentanones
cycloheptanones.
reaction
mechanism
was
investigated
DFT
calculation
origins
regioselectivities
were
rationalized.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(44), С. 23641 - 23645
Опубликована: Сен. 8, 2021
The
asymmetric
synthesis
of
2,2-difluorinated
tetrahydrofurans
was
accomplished
via
enantioselective
formal
[3+2]
cycloaddition
catalyzed
by
palladium.
reaction
between
gem-difluoroalkenes
and
racemic
vinyl
epoxides
or
vinylethylene
carbonates
resulted
in
the
formation
enantioenriched
2,2-difluorotetrahydrofurans
with
an
enantioselectivity
up
to
98
%.
Notably,
used
readily
available
(R)-BINAP
as
ligand
at
a
low
loading
yielded
wide
variety
difluorinated
products
moderate
high
yields.
Both
chiral
diastereomers
could
be
obtained
single
sequence.
