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.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 5980 - 5992
Опубликована: Янв. 1, 2024
N
-Cyano
iminophosphoranes
are
synthesized
using
electrochemistry
and
evaluated
as
ligands
in
various
nickel-catalysed
reactions.
The
electronic
structural
properties
of
these
were
studied
both
computationally
experimentally.
Herein,
we
report
the
concise
total
syntheses
of
(+)-leucolusine
and
(-)-7-epi-leucolusine
achieved
in
8
steps
starting
from
commercially
available
piperidin-2-one.
Our
strategy
highlights
a
palladium-catalyzed
decarboxylative
asymmetric
allylic
alkylation
for
constructing
δ-lactam
bearing
C20
all-carbon
quaternary
stereocenter.
Additionally,
cis-fused
octahydrofuro[2,3-b]pyridine
unit
was
efficiently
constructed
via
one-pot
protocol
encompassing
reduction
oxa-Mannich-type
cyclization
processes.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(46)
Опубликована: Май 16, 2024
The
Pd-catalysed
decarboxylative
asymmetric
allylic
alkylation
(DAAA)
has
been
applied
to
the
enantioselective
synthesis
of
sterically
hindered
benzofuran-3(2H)-one-derived
α-aryl-β-keto
esters
employing
(R,R)-ANDEN
phenyl
Trost
ligand.
A
range
substrates
were
synthesised,
previously
developed
aryllead
triacetate
methodology
install
various
aryl
groups.
resulting
α-aryl-α-allyl
benzofuran-3(2H)-one
DAAA
products
obtained
in
moderate
high
yields
and
enantioselectivities
up
96
%
ee,
with
best
results
observed
for
containing
a
di-ortho-substitution
pattern
on
ring
as
well
naphthyl-containing
substrates.
Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9185 - 9190
Опубликована: Окт. 18, 2024
In
the
presence
of
Wilkinson's
catalyst,
N-sulfinyl
metalloenamines
derived
from
NH-deprotonation
β,β-disubstituted
enesulfinamides
undergo
nucleophilic
allylic
substitution
with
allyl
carbonate,
affording
α-allylated
ketimines
high
stereoselectivity.
These
allylation
products
possess
challenging
acyclic
quaternary
stereocenters
containing
one
group
and
two
alkyl
groups
that
are
both
sterically
electronically
similar
(e.g.,
Me
Et).
By
utilizing
appropriate
stereoisomers
enesulfinamides,
it
becomes
feasible
to
selectively
access
each
four
potential
products,
thereby
facilitating
selective
synthesis
α-tertiary
chiral
amines
featuring
a
β-quaternary
stereocenter
through
imino
addition.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(21), С. 4497 - 4502
Опубликована: Июль 31, 2024
Abstract
Monophosphine
ligands
based
on
C−N
axially
chiral
N
‐Arylpyrrole
backbones
are
prepared
starting
from
amino
acids
and
evaluated
in
Pd‐catalyzed
asymmetric
allylic
substitutions.
20.7–99.9%
ees
achieved
the
reactions
of
rac
‐1,3‐diphenylallyl
acetates
with
O−,
N−
C‐nucleophiles.
Ligand
screening
revealed
that
steric
hindrance
3‐
or
4‐
position
pyrrole
is
crucial
for
enantioselectivity
reaction.
The
synthetic
utilization
products
was
demonstrated
by
transformation
one
product
a
gold‐catalyzed
oxidative
rearrangement
Pharmaceutical Fronts,
Год журнала:
2024,
Номер
06(03), С. e237 - e251
Опубликована: Авг. 6, 2024
Chiral
polyheterocycles
represent
an
important
class
of
compounds
because
their
prevalence
in
bioactive
natural
products
and
chiral
drugs.
Pd-catalyzed
allylic
substitution
is
a
powerful
synthetic
tool
for
forming
C–C
C–X
bonds
(X
=
N,
O,
S,
etc.).
Naturally,
asymmetric
cascade
reactions
that
utilize
are
undoubtedly
efficient
pathways
to
construct
heterocycles.
In
this
article,
we
reviewed
the
via
desymmetrization
meso-diol
diesters
cycloolefins,
construction
derivatives.
Herein
we
describe
the
organocatalytic
asymmetric
allylic
benzylborylation
of
allyl
fluorides
with
α-silyl
benzylboronic
esters.
The
catalytic
protocol
leverages
singular
features
fluoride
as
an
unconventional
leaving
group,
enabling
generation
reactive
α-boryl
carbanion
species
through
desilylative
activation.
It
allows
construction
a
wide
set
homoallylic
benzylated
organoboronates
bearing
two
contiguous
stereocenters.
chiral
boronate
installed
in
products
serves
synthetic
lynchpin
to
construct
complex
chemical
architectures
stereospecific
manner.
