Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 31, 2024
ConspectusPalladium
catalysis,
as
one
of
the
most
important
strategies
in
asymmetric
synthesis,
has
continuously
attracted
attention
organic
chemists.
With
development
chiral
ligands,
increasingly
challenging
reactions
and
substantial
progress
catalysis
are
being
realized.Since
2014,
we
have
focused
on
exploiting
a
series
sulfinamide
phosphine
ligands
called
"Sadphos,"
including
Ming-Phos,
Xu-Phos,
Xiao-Phos,
Xiang-Phos,
TY-Phos,
PC-Phos,
GF-Phos,
WJ-Phos.
These
can
be
easily
prepared
two
to
four
steps
using
commercial
materials.
new
types
shown
remarkable
performance
transition-metal-catalyzed
reactions,
especially
Pd-catalyzed
transformations.
X-ray
diffraction
analysis,
mechanistic
studies,
density
functional
theory
calculations
revealed
that
Sadphos
coordinate
with
Pd0
PdII
species
Pd0/P,
Pd0/P,S,
or
PdII/P,O
modes.This
Account
summarizes
our
recent
efforts
toward
palladium-catalyzed
enantioselective
ligands.
were
found
privileged
very
crucial
promote
by
increasing
reactivity
enantioselectivity.
Ming-Phos
is
an
effective
ligand
coupling
intramolecular
Heck
providing
highly
trisubstituted
allenes,
axially
anilides,
gem-diarylmethine
silanes,
disubstituted
dihydroisoquinolinones.
Incorporation
electron-rich
cyclohexyl
group
moiety
afforded
which
showed
unique
effect
transformations,
reductive
Heck,
dearomative
Mizoroki–Heck,
tandem
Heck/Suzuki
coupling,
carboiodination,
carboamination,
cross-coupling
reactions.
Using
similar
strategy,
synthesized
more
electron–rich
TY-Phos
Xiang-Phos
bearing
t-butyl
1-adamantyl
at
P
atoms,
respectively.
Regarding
stereoelectronic
features,
these
characteristic
best
choice
satisfy
requirements
fluoroarylation
gem-difluoroalkenes,
intermolecular
α-arylation
aldehydes,
carboetherification
alkenyl
oximes,
carboheterofunctionalization
2,3-dihydrofurans.
Compared
aforementioned
attractive
features
high
nucleophilicity
originating
from
CH2PPh2
ortho-substituent
side
aryl
ring,
presumably
responsible
for
its
efficiency.
The
Pd/Xiao-Phos
catalyst
system
shows
good
secondary
oxides,
affording
P-stereogenic
products
multiple
molecular
skeletons.
modification
basic
backbone
introducing
xanthene
skeleton
motivated
us
design
synthesize
monophosphines,
named
PC-Phos
GF-Phos.
various
arylation
sulfenate
anions,
denitrogenative
cyclization
benzotriazoles,
dearomatization
indoles.
practicability
GF-Phos
was
validated
three-component
N-tosylhydrazones,
halides,
terminal
alkynes,
well
N-tosylhydrazones
vinyl
iodides
pendent
amines.
In
addition,
ferrocene-derived
WJ-Phos
employed
Suzuki–Miyaura
reaction,
biaryl
monophosphine
oxides
excellent
enantiomeric
excesses.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21231 - 21238
Опубликована: Июль 29, 2024
Asymmetric
Pd-catalyzed
three-component
carboamination
reactions
of
dienes
to
construct
chiral
cyclohexenylamines,
which
are
great
importance
in
many
fields
chemistry,
have
remained
largely
unexplored.
Here,
we
demonstrate
a
highly
enantio-
and
regioselective
Pd/Ming-Phos-catalyzed
1,3-cyclohexadiene
with
readily
available
aryl
iodides
anilines
for
facile
access
diverse
valuable
cyclohexenylamines.
The
process
shows
excellent
functional
group
tolerance,
easy
scalability,
mild
conditions.
Moreover,
mechanistic
studies
suggest
that
this
reaction
has
first-order
dependence
on
the
concentration
palladium
catalyst
aniline.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Enantioselective
synthesis
of
isoxazolines
bearing
allenes
by
palladium
catalyzed
carboetherification
alkenyl
oximes
with
propargylic
acetates.
DFT
calculations
carried
out
to
disclose
the
detailed
mechanism
and
origins
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Фев. 21, 2024
As
a
type
of
elementary
organic
compounds
containing
N-N
single
bond,
hydrazone
involved
chemical
conversions
are
extremely
extensive,
but
they
mainly
limited
to
N
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9176 - 9180
Опубликована: Дек. 19, 2023
An
electroreductive
carboxylation
of
propargylic
alcohols
with
CO2
and
then
workup
TMSCHN2
to
construct
tetrasubstituted
2,3-allenoates
is
developed.
This
method
allows
the
incorporation
an
external
ester
group
into
resulting
allene
system
through
electroreduction,
carboxylation,
deacetoxylation
cascades.
Mechanistically,
electricity
on/off
experiments
cyclic
voltammetry
analysis
support
preferential
generation
radical
anion
or
3-aryl
acetate
based
on
electron
nature
aryl
rings.
Organic Letters,
Год журнала:
2023,
Номер
25(25), С. 4682 - 4687
Опубликована: Июнь 19, 2023
A
highly
efficient
Pd-catalyzed
carboetherification
reaction
of
β,γ-unsaturated
ketoximes
with
propargylic
acetates
is
demonstrated.
This
method
provides
a
practical
protocol
for
accessing
the
incorporation
an
allene
moiety
into
3,5-disubstituted
and
3,5,5-trisubstituted
isoxazolines.
The
salient
features
this
transformation
include
broad
substrate
scope,
good
functional
group
tolerance,
easy
scale-up,
versatile
transformations,
applications
in
late-stage
modification
drugs.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2768 - 2773
Опубликована: Янв. 1, 2024
Synthesis
of
isoxazolines
and
dihydrooxazines
bearing
an
alkyne
group
by
Pd-catalyzed
oxyalkynylation
alkenyl
oximes
with
alkynyl
bromides.
This
new
approach
has
a
broad
substrate
scope
good
functional
tolerance.
Chemical Science,
Год журнала:
2024,
Номер
15(24), С. 9192 - 9200
Опубликована: Янв. 1, 2024
A
series
of
bicyclic
products
containing
dihydrofuran
and
tetrahydrofuran
skeletons
were
obtained
by
divergent
palladium-catalyzed
selective
C–C
bond
cleavage
keto-VDCPs.
The
reaction
mechanism
was
also
investigated
systematically.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Herein,
we
reported
a
palladium-catalysed
alleneamination
of
γ,δ-unsaturated
hydrazones
with
propargylic
acetates,
which
provides
an
efficient
approach
for
the
synthesis
tetrahydropyridazine
bearing
allenes
in
moderate
to
good
yields.
Organic Letters,
Год журнала:
2024,
Номер
26(19), С. 4031 - 4036
Опубликована: Янв. 26, 2024
We
present
a
new
[3+2]
cycloaddition
reaction
between
alkyl-acceptor
diazoalkanes
under
visible
light
irradiation.
By
employing
easily
accessible
alkyl-acceptor-type
or
their
precursor
hydrazones
as
both
1,3-dipoles
and
dipolarophiles,
diverse
range
of
pyrazoline
derivatives
featuring
quaternary
center
have
been
efficiently
synthesized
in
predictable
manner,
with
excellent
functional
group
tolerance
good
yields.
Furthermore,
scale-up
experiments
downstream
transformations
the
product
were
also
detailed.
