Angewandte Chemie,
Год журнала:
2024,
Номер
136(22)
Опубликована: Март 23, 2024
Abstract
Despite
the
significance
of
chiral
allene
skeletons
in
catalysis,
organic
synthesis
and
medicinal
chemistry
et
al.,
there
is
a
scarcity
reports
on
axially
allenyl
phosphorus
compounds.
Here,
we
disclosed
an
efficient
straightforward
cascade
reaction
between
ethynyl
ketones
phosphine
oxides,
resulting
broad
array
trisubstituted
allenes
incorporating
moiety
high
yields
with
excellent
stereoselectivities
facilitated
by
peptide‐mimic
phosphonium
salt
(PPS)
Additionally,
comprehensive
series
mechanistic
experiments
have
been
conducted
to
elucidate
that
this
proceeds
via
asymmetric
Pudovik
addition
followed
subsequent
phospha
‐Brook
rearrangement
occurs
concomitantly
kinetic
resolution,
representing
stereospecific
protonation
process
facilitating
central‐to‐axial
chirality
transfer
manner.
We
anticipate
our
research
will
pave
way
for
promising
exploration
novel
stereo‐induction
pattern
addition/
reaction.
Chemical Science,
Год журнала:
2023,
Номер
14(28), С. 7709 - 7715
Опубликована: Янв. 1, 2023
A
novel
three-component
protocol
to
synthesize
trisubstituted
allenes
from
2-alkynyl-1,4-diol
dicarbonate
with
organoboronic
acid
and
malonate
has
been
developed.
Abstract
Transition
metal‐catalyzed
synthesis
of
propargylic
esters
has
been
widely
investigated,
offering
distinctive
opportunities
to
build
1,3‐diene
skeletons.
Access
1,2,3,4‐tetrasubstituted
1,3‐dienes
a
longstanding
challenge
in
organic
due
great
diversity
stereoisomers
from
four
substituents
and
unpredictable
regioselectivity.
Given
the
synthetic
challenges
importance,
inventing
methods
for
generation
this
valuable
architecture
gathered
much
more
attention.
Recently,
several
intriguing
works
concerning
topic
have
achieved
towards
high
regio‐
stereoselective
elaborate
1,3‐dienes.
Herein,
concept
summarizes
recent
advances
transition
construction
discusses
mechanism
as
well
their
applications.
Organic Letters,
Год журнала:
2023,
Номер
25(39), С. 7105 - 7109
Опубликована: Сен. 21, 2023
Highly
enantioselective
propargyl
Claisen
rearrangement
of
O-propargyl
β-ketoesters
was
achieved
under
2.5
mol
%
the
chiral
cobalt
complex
as
catalyst
mild
reaction
conditions.
With
Co(OTf)2
Lewis
acid
and
C1-symmetric
imidazoline-pyrroloimidazolone
pyridine
ligand,
diverse
allenyl-substituted
all-carbon
quaternary
were
obtained
in
good
yields
(up
to
97%
yield)
high
enantioselectivities
98%
ee).
Angewandte Chemie,
Год журнала:
2024,
Номер
136(22)
Опубликована: Март 23, 2024
Abstract
Despite
the
significance
of
chiral
allene
skeletons
in
catalysis,
organic
synthesis
and
medicinal
chemistry
et
al.,
there
is
a
scarcity
reports
on
axially
allenyl
phosphorus
compounds.
Here,
we
disclosed
an
efficient
straightforward
cascade
reaction
between
ethynyl
ketones
phosphine
oxides,
resulting
broad
array
trisubstituted
allenes
incorporating
moiety
high
yields
with
excellent
stereoselectivities
facilitated
by
peptide‐mimic
phosphonium
salt
(PPS)
Additionally,
comprehensive
series
mechanistic
experiments
have
been
conducted
to
elucidate
that
this
proceeds
via
asymmetric
Pudovik
addition
followed
subsequent
phospha
‐Brook
rearrangement
occurs
concomitantly
kinetic
resolution,
representing
stereospecific
protonation
process
facilitating
central‐to‐axial
chirality
transfer
manner.
We
anticipate
our
research
will
pave
way
for
promising
exploration
novel
stereo‐induction
pattern
addition/
reaction.
