Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(69)
Опубликована: Сен. 18, 2023
A
formal
palladium-catalyzed
decarboxylative
(4+2)
cycloaddition
reaction
between
4-vinylbenzoxazinanones
and
2-nitro-1,3-enynes
has
been
developed
to
produce
highly
valuable,
densely
functionalized
tetrahydroquinolines
in
moderate
excellent
yields
with
high
diastereoselectivity
under
mild
conditions.
The
optimised
protocol
tolerates
a
range
of
substituted
2-nitro-1,3-enynes,
which
represent
an
under-utilized
class
dipolarophile
for
transition-metal
catalyzed
cycloadditions.
employed
methodology
facilitates
efficient
both
N-H-
N-Ts-4-vinylbenzoxazinanone
dipole
precursors.
stereochemistry
the
major
minor
diastereomeric
cycloadducts
was
determined
by
single
crystal
X-ray
analyses.
mechanistic
rationale
intrinsic
preliminary
enantioselective
experiments
are
also
presented.
tetrahydroquinoline
cycloadduct
products
feature
numerous
pendant
functionalities,
including
vinyl
handle,
internal
alkyne
motif
nitro
functionality
(which
functions
as
latent
C-3
nitrogen
substituent)
further
synthetic
manipulations.
ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2746 - 2757
Опубликована: Фев. 7, 2024
Remote
stereocontrol
in
transition-metal
catalysis
is
a
challenging
but
interesting
research
topic.
In
this
work,
we
achieved
copper-catalyzed
asymmetric
yne-allylic
substitution
using
electron-rich
arenes
and
acyclic
carbonates
through
remote
enantioselectivity
control.
The
reaction
delivers
variety
of
enantioenriched
products
that
contain
diverse
set
valuable
moieties,
such
as
conjugated
enynes,
indoles,
indolizines,
allenes,
dihydrofurans,
which
are
widely
used
organic
synthesis
act
key
units
bioactive
molecules
natural
products.
synthetic
value
protocol
has
been
demonstrated
series
further
transformations,
mechanistic
studies
have
conducted
to
gain
more
insight
into
the
reaction.
ACS Catalysis,
Год журнала:
2022,
Номер
12(7), С. 4046 - 4053
Опубликована: Март 16, 2022
Gold(I)
complexes
of
a
chiral
phosphoric
acid-functionalized
phosphine
the
CPA-Phos
series
enable
enantioselective
multicomponent
reactions
between
aldehydes,
hydroxylamines
and
cyclic
yne-enones,
leading
to
3,4-dihydro-1H-furo[3,4-d][1,2]oxazines.
This
represents
rare
example
highly
reaction
in
gold(I)
catalysis.
The
proceed
at
low
catalyst
loading
provide
high
yields,
total
diastereoselectivity,
enantiomeric
excesses
up
99%.
Silver-free
conditions
can
be
applied.
method
has
very
broad
scope
as
it
applies
both
aliphatic
aromatic
aldehydes
hydroxylamines,
variety
yne-enone-derived
oximes.
DFT
calculations
complement
this
study
enlighten
reactivity
issues
mechanistic
pathways.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(27)
Опубликована: Май 2, 2022
A
highly
enantioselective
tandem
Pudovik
addition/[1,2]-phospha-Brook
rearrangement
of
α-alkynylketoamides
with
diarylphosphine
oxides
was
achieved
a
N,N'-dioxide/ScIII
complex
as
the
catalyst.
This
protocol
features
broad
substrate
scope,
high
regio-
and
enantioselectivity,
good
functional-group
compatibility,
providing
straightforward
route
to
various
trisubstituted
allenes
diarylphosphinate
functionality
in
yields
enantioselectivities
(up
97
%
yield,
96
ee).
Control
experiments
theoretical
calculations
revealed
that
synergistic
effect
counterion
water
critical
for
protonation
after
[1,2]-phospha-Brook
rearrangement.
The
synthetic
utility
this
methodology
demonstrated
by
conversion
products
into
bridged
polycyclic
architectures
through
intramolecular
dearomatizing
arene/allene
cycloaddition.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 2142 - 2148
Опубликована: Янв. 25, 2023
Allenol
has
been
identified
as
a
versatile
building
block
for
organic
synthesis,
and
numerous
efforts
have
made
to
synthesize
apply
allenol.
However,
limited
obtain
trifluoromethyl-substituted
Here,
by
using
readily
available
1,3-enyne
the
starting
material,
copper-catalyzed
trifluoromethylbenzoxylation
process
was
developed
efficient
synthesis
of
allenols
Togni-II
reagent
reaction
partner.
Triple
roles
reagent,
including
source
trifluoromethyl
group,
hydroxyl
oxidant,
were
elucidated
in
this
transformation.
Moreover,
late-stage
diversification
performed,
which
revealed
application
potential
preparation
various
compounds.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1770 - 1775
Опубликована: Март 1, 2024
Abstract
We
report
herein
an
enantioselective
[3+3]
annulation
of
indoline‐2‐thiones
with
yne–enones
by
chiral
dinuclear
zinc
catalysts
via
a
Brønsted
base
and
Lewis
acid
cooperative
activation
model.
This
transformation
proceeded
through
sequential
conjugate
addition,
allenyl
ketone
formation
intramolecular
sulfa‐Michael
6‐
endo
‐trig
cyclization.
A
range
enantioenriched
tetrahydrothiopyrano[2,3‐
b
]indole
derivatives
bearing
exocyclic
double
bond
were
obtained
in
moderate
yields
excellent
stereoselectivities
(up
to
20
:
1
dr,
20:1
Z/E
ratio
95%
ee).
Late‐stage
functionalization,
large‐scale
experiment
further
derivatizations
also
explored.
Abstract
The
1,
n
‐enynes
are
potent
scaffolds
in
organic
synthesis,
providing
a
state‐of‐the‐art
approach
for
synthesizing
various
acyclic
and
carbo‐
heterocyclic
compounds.
Radical
cascade
cyclization
C−H
functionalization
of
have
gained
immense
attention
the
synthetic
community.
Significant
advancement
this
field
has
been
developed
over
years,
employing
harsh
expensive
metal
catalysts
usually
associated
with
intense
product
purification
unwanted
side‐products.
In
context,
advent
visible
light
photocatalysis
as
mild
efficient
area
is
welcome
step.
Herein,
we
provide
an
exclusive
overview
recent
developments
light‐assisted
manipulation
‐enynes.
We
classified
review
into
1,3‐,
1,4‐,
1,5‐,
1,6‐,
1,7‐,
1,8‐enynes,
well
dienyne,
enediyne‐based
reactions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(10), С. 5624 - 5630
Опубликована: Март 2, 2023
A
cooperative
catalyst
system
involving
a
Pd(0)/Senphos
complex,
tris(pentafluorophenyl)borane,
copper
bromide,
and
an
amine
base,
is
demonstrated
to
catalyze
trans-hydroalkynylation
of
internal
1,3-enynes.
For
the
first
time,
Lewis
acid
shown
promote
reaction
emerging
outer-sphere
oxidative
step.
The
resulting
cross-conjugated
dieneynes
are
versatile
synthons
for
organic
synthesis,
their
characterization
reveals
distinct
photophysical
properties
depending
on
positioning
donor/acceptor
substituents
along
conjugation
path.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(35)
Опубликована: Июль 4, 2022
Abstract
We
designed
a
borane/gold(I)
co‐catalytic
system
and
used
it
for
C−H
functionalization
reactions
cycloaddition
between
tertiary
amines
α‐alkynylenones.
Both
effectively
incorporated
furan
ring
into
the
amine.
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3790 - 3795
Опубликована: Апрель 26, 2024
A
cooperative
gold(I)/DMAP
system
catalyzes
the
(2
+
3)
cycloadditions
of
yne-enones
with
oxindole-derived
Morita-Baylis-Hillman
(MBH)
carbonates,
yielding
diverse
bispiro-cyclopentene
oxindole
products.
The
mild,
scalable
protocol
demonstrates
broad
substrate
scope
and
excellent
chemo-
diastereoselectivity.
Mechanistic
study
reveals
pivotal
roles
both
catalysts
in
unique
cycloaddition.
This
strategy
showcases
superiority
achieving
transformation
chemoselectivity
diastereoselectivity,
unattainable
through
traditional
monocatalytic
methodologies.
