Angewandte Chemie,
Год журнала:
2021,
Номер
133(39), С. 21426 - 21430
Опубликована: Июль 8, 2021
Abstract
Dynamic
kinetic
asymmetric
transformation
(DYKAT)
reactions
of
racemic
diastereomer
mixtures
that
afford
the
products
as
essentially
single
diastereomers
with
high
enantioselectivities
are
described.
We
demonstrated
DYKAT
in
diastereo‐
and
enantioselective
synthesis
spirooxindoles
bearing
furan‐fused
rings.
The
starting
materials
DYKAT,
dihydrobenzofuranone
derivatives,
were
synthesized
mixtures,
these
transformed
to
spirooxindole
derivatives
yields
through
Michael–Henry
cascade
nitrostyrenes
under
organocatalytic
conditions.
In
reactions,
regardless
stereochemistry
materials,
all
four
isomers
enantioselectivities,
new
chiral
centers
created.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июль 29, 2021
Abstract
The
simultaneous
construction
of
two
different
chiralities
via
a
simple
operation
poses
considerable
challenge.
Herein
cationic
gold-catalyzed
asymmetric
hydroarylation
ortho-alkynylaryl
ferrocenes
derivatives
is
developed,
which
enable
the
axial
and
planar
chirality.
here
identified
TY-Phos
derived
gold
complex
responsible
for
high
yield,
good
diastereoselectivity
(>20:1
dr),
enantioselectivities
(up
to
99%
ee)
mild
conditions.
catalyst
system
also
shows
potential
application
in
synthesis
chiral
biaryl
compounds.
cause
enantioselectivity
this
investigated
with
density
functional
theory
caculation.
Abstract
Oxazocines
are
key
structural
intermediates
in
the
synthesis
of
natural
products
and
pharmaceutical
molecules.
However,
oxazocines
especially
a
highly
enantioselective
manner,
is
long‐standing
formidable
challenge
due
to
unfavorable
energetics
involved
cyclization.
Herein,
series
new
PNP‐Ligand
P
‐chiral
stereocenter
first
designed
synthesized,
called
MQ‐Phos
,
successfully
applied
it
Pd‐catalyzed
higher‐order
formal
[4+4]‐cycloaddition
α
β
‐unsaturated
imines
with
2‐(hydroxymethyl)‐1‐arylallyl
carbonates.
The
reaction
features
mild
conditions,
excellent
regio‐
enantiocontrol
broad
substrate
scope
(54
examples).
Various
medium‐sized
rings
can
be
afforded
moderate
yields
(up
92%)
enantioselectivity
99%
ee).
newly
developed
critical
for
ring
catalytic
reactivity
enantioselectivity.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(22), С. 6330 - 6336
Опубликована: Янв. 1, 2021
An
organocatalytic
asymmetric
dearomative
[4
+
2]
annulation
of
2-nitrobenzofurans
and
5
H
-thiazol-4-ones
is
developed
for
the
construction
dihydrobenzofuran-bridged
polycyclic
skeletons
with
good
results.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(21), С. 6067 - 6073
Опубликована: Янв. 1, 2021
An
unprecedented
palladium-catalyzed
asymmetric
carbonylation
of
ArI
with
carbon
monoxide
(CO)
to
expand
a
class
atroposelective
cyclic
and
acyclic
amides
in
good
yields
high
enantioselectivities
has
been
reported.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 26, 2022
Abstract
Dearomatized
indole
derivatives
bearing
a
C3‐
or
C2‐stereocenter
exist
ubiquitously
in
natural
products
and
biologically
active
molecules.
Despite
remarkable
advances
their
synthesis,
stereoselective
regio‐divergent
methods
are
still
high
demand.
Herein,
Pd‐catalyzed
intermolecular
asymmetric
spiroannulation
of
2,3‐disubstituted
indoles
with
internal
alkynes
has
been
developed
for
the
efficient
construction
indoline
structures
C2‐quaternary
stereocenter.
Stereospecific
aza‐semipinacol
rearrangement
these
under
acidic
conditions
afforded
indolenine
C3‐quaternary
stereocenter,
where
migrating
group
could
be
controlled
by
reaction
sequence.
The
together
subsequent
enabled
divergent
access
to
dearomatized
either
Chemical Science,
Год журнала:
2021,
Номер
12(30), С. 10388 - 10394
Опубликована: Янв. 1, 2021
The
spiroindimicins
are
a
unique
class
of
chlorinated
indole
alkaloids
characterized
by
three
heteroaromatic
rings
structured
around
congested
spirocyclic
stereocenter.
Here,
we
report
the
first
total
synthesis
(+)-spiroindimicin
A,
which
bears
challenging
C-3'/C-5''-linked
spiroindolenine.
We
detail
our
initial
efforts
to
effect
biomimetic
oxidative
spirocyclization
from
its
proposed
natural
precursor,
lynamicin
D,
and
describe
how
these
studies
shaped
final
abiotic
9-step
solution
this
complex
alkaloid
built
key
Pd-catalyzed
asymmetric
spirocyclization.
Scalable
access
H,
their
congeners
has
enabled
discovery
activity
against
several
parasites
relevant
human
health,
providing
potential
starting
points
for
new
therapeutics
neglected
tropical
diseases
leishmaniasis
African
sleeping
sickness.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(3), С. 270 - 294
Опубликована: Янв. 10, 2023
Abstract
Dearomatization
reactions
are
among
the
most
efficient
chemical
processes,
combining
atom
economy,
stereospecificity
and
ability
to
generate
molecular
complexity
in
a
single
step.
Dearomative
vinylation
provide
synthetic
connection
between
readily
available,
simple
aromatic
starting
materials
more
unsaturated
alkynes.
The
last
decade
has
witnessed
steady
increase
development
of
transition
metal‐catalyzed
dearomative
methods
electron
rich
compounds
with
alkynes,
providing
new
approaches
high‐value
building
blocks
natural
products.
This
review
aims
serve
as
comprehensive
reference
for
work
magnified
image
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(41), С. 22184 - 22188
Опубликована: Июль 17, 2021
Abstract
Herein
we
report
a
Pd‐catalyzed
dearomative
methoxyallylation
of
3‐nitroindoles
with
readily
available
allyl
carbonates.
Good
yields
(up
to
86
%)
and
diastereoselectivity
>20:1
dr)
are
obtained
for
wide
range
substrates.
The
compatibility
gram‐scale
synthesis
the
relatively
low
catalyst
loading
(down
1
mol
%
[Pd])
enhance
practicality
this
method.
kinetic
experiments
indicate
that
rate‐determining
step
reaction
is
nucleophilic
attack
alkoxide
anion.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(29)
Опубликована: Май 12, 2022
The
asymmetric
catalytic
addition
of
linear
Grignard
reagents
to
ketones
has
been
a
long-standing
challenge
in
organic
synthesis.
Herein,
novel
family
PNP
ligands
(W-Phos)
was
designed
and
applied
copper-catalyzed
aryl
alkyl
ketones,
allowing
facile
access
versatile
chiral
tertiary
alcohols
good
high
yields
with
excellent
enantioselectivities
(up
94
%
yield,
96
ee).
process
can
also
be
used
synthesize
allylic
from
more
challenging
α,β-unsaturated
ketones.
Notably,
the
potential
utility
this
method
is
demonstrated
gram-scale
synthesis
modification
various
densely
functionalized
medicinally
relevant
molecules.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(39), С. 21256 - 21260
Опубликована: Июль 8, 2021
Dynamic
kinetic
asymmetric
transformation
(DYKAT)
reactions
of
racemic
diastereomer
mixtures
that
afford
the
products
as
essentially
single
diastereomers
with
high
enantioselectivities
are
described.
We
demonstrated
DYKAT
in
diastereo-
and
enantioselective
synthesis
spirooxindoles
bearing
furan-fused
rings.
The
starting
materials
DYKAT,
dihydrobenzofuranone
derivatives,
were
synthesized
mixtures,
these
transformed
to
spirooxindole
derivatives
yields
through
Michael-Henry
cascade
nitrostyrenes
under
organocatalytic
conditions.
In
reactions,
regardless
stereochemistry
materials,
all
four
isomers
enantioselectivities,
new
chiral
centers
created.
