Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 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.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(7), P. 1212 - 1222
Published: March 9, 2022
Abstract
Axially
chiral
allenes
occur
on
a
wide
range
of
natural
products
and
synthetic
molecules
with
significant
biological
activity.
Furthermore,
they
are
versatile
building
blocks
in
organic
synthesis
because
their
inherent
chemical
properties.
Accordingly,
catalytic
enantioselective
axially
has
been
paid
much
attention.
Benefited
from
the
development
asymmetric
organocatalysis,
many
simple
efficient
methods
terms
different
systems
as
well
reaction
partners
have
developed.
This
review
will
focus
recent
progress
field
organocatalytic
(2000–2022),
which
is
organized
according
to
types
catalyst
system
used.
magnified
image
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(31)
Published: June 1, 2023
The
skeletons
of
chiral
tetrasubstituted
allenes
bearing
a
vicinal
all-carbon
quaternary
stereocenter
are
importance
but
still
challenging
to
synthesize.
Herein,
we
report
enantio-
and
diastereoselective
γ-additions
1-alkynyl
ketimines
with
dual-copper-catalysis
under
mild
conditions,
affording
α-amino
allenoates
in
high
yields
(up
99
%
yield)
excellent
enantioselectivities
ee)
diastereoselectivities
>20
:
1
dr).
Importantly,
the
stereodivergent
synthesis
products
was
realized
by
asymmetric
γ-addition
reaction
Grignard
reagent
promoted
epimerization.
Moreover,
dual-copper-catalyzed
reactions
were
smoothly
applied
gram-scale
adopted
introduce
allenyl
moieties
into
bioactive
molecules.
Mechanistic
experiments
density
functional
theory
(DFT)
calculations
demonstrated
that
catalyzed
double
copper
catalysts.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(22), P. 11165 - 11206
Published: Jan. 1, 2024
This
review
explores
the
fascinating
world
of
molecules
featuring
multiple
stereogenic
elements,
unraveling
different
strategies
designed
over
years
for
their
enantioselective
synthesis.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(27), P. 4914 - 4918
Published: June 30, 2022
An
asymmetric
organocatalytic
remote
1,10-addition
of
alkynyl
indole
imine
methides
generated
in
situ
from
α-(6-indolyl)
propargylic
alcohols
with
thiazolones
has
been
developed
for
the
first
time,
affording
axially
chiral
tetrasubstituted
allenes
featuring
vicinal
sulfur-containing
quaternary
carbon
stereocenters
high
yields
excellent
stereoselectivities.
The
representative
scale-up
reaction
and
transformations
1,10-adduct
were
examined.
mechanism
was
expounded
by
control
experiments
DFT
calculations.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2068 - 2072
Published: March 20, 2023
The
organocatalytic
asymmetric
reactions
of
C2-unsubstituted
racemic
naphthyl-indoles
with
orthoalkynylnaphthols
were
employed
to
synthesize
axially
chiral
styrenes
connected
an
naphthyl-indole
unit.
Utilizing
phosphoric
acid
as
the
catalyst,
these
prepared
in
good
yields
(up
96%)
and
excellent
stereoselectivity
>99.9%
ee,
>20:1
dr,
>99:1
E/Z)
mild
conditions.
Moreover,
further
synthetic
transformations
achieved
high
stereocontrol.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(13), P. 2323 - 2327
Published: March 30, 2023
Herein,
successful
utilization
of
non-covalent
N-heterocyclic
carbene
(NHC)
catalysis
toward
asymmetric
aminative
dearomatization
naphthols
is
presented.
The
NHC-catalyzed
process
offers
enantioselective
synthesis
cyclic
enones
possessing
a
nitrogen-containing
α-quaternary
stereocenter.
reaction
applies
to
various
functionalized
substrates
including
acid-labile
groups
and
shown
be
scalable.
Substrate
activation
via
an
O-H···NHC
hydrogen-bonding
interaction
suggested
based
on
the
results
obtained
in
mechanistic
studies.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(7), P. 1376 - 1381
Published: Feb. 13, 2024
We
report
a
Cu(I)–Ph-BPE-catalyzed
asymmetric
vinylogous
Mannich
reaction
of
β,γ-alkynyl-α-ketimino
esters
with
β,γ-unsaturated
N-acylpyrazoles.
In
this
process,
the
Cu(I)–Ph-BPE
catalyst
activates
ester
through
N,O-coordination,
enabling
subsequent
nucleophilic
addition
dienolate
generated
from
N-acylpyrazole
via
α-position
deprotonation
catalytic
amount
tertiary
amine.
The
reactions
gave
useful
products
very
high
enantioselectivities.
A
broad
range
substrates
various
substituents
are
tolerated
in
reaction.
versatility
method
was
demonstrated
by
gram-scale
reaction,
and
elaboration
adducts
also
provided.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 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,
Journal Year:
2024,
Volume and Issue:
15(11), P. 3831 - 3871
Published: Jan. 1, 2024
In
the
vast
majority
of
top-selling
pharmaceutical
and
industrial
products,
phenolic
structural
motifs
are
highly
prevalent.
Non-functionalized
simple
phenols
serve
as
building
blocks
in
synthesis
value-added
chemicals.
It
is
worth
mentioning
that
lignin,
being
largest
renewable
biomass
source
aromatic
nature,
mainly
consists
units,
which
enable
production
structurally
diverse
phenols.
Given
their
remarkable
applicability
chemical
value
chain,
many
efforts
have
been
devoted
to
increasing
molecular
complexity
scaffold.
Among
key
techniques,
direct
functionalization
Csp
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(22), P. 4058 - 4063
Published: May 25, 2022
We
developed
a
novel
asymmetric
Friedel-Crafts
alkylation/transamidation
tandem
reaction
for
the
enantio-
and
diastereoselective
synthesis
of
pyrazolo[3,4-b]pyridin-6-ones
bearing
-CF3
unit
via
synergistic
chiral
phosphoric
acid
MgSO4
catalysis.
This
[3
+
3]
annulation
protocol
allows
formation
trifluoromethylated
with
two
adjacent
tertiary
stereocenters
in
moderate
to
high
yields
(up
90%),
enantioselectivities
97%
ee),
diastereoselectivities
>20:1
dr).
