Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(47), P. 24930 - 24940
Published: Oct. 11, 2021
By
virtue
of
a
fundamentally
new
reaction
model
azomethine
ylide
serving
as
two-atom
synthon,
we
present
the
first
example
stereodivergent
preparation
γ-butyrolactones
via
synergistic
Cu/Ir-catalyzed
asymmetric
cascade
allylation/lactonization,
and
all
four
stereoisomers
bearing
two
vicinal
stereocenters
are
accessible
with
excellent
diastereoselective
enantioselective
control.
The
chiral
IrIII
-π-allyl
intermediate
was
separated
characterized
to
understand
origin
regio-
stereoselectivity
initial
C-C
bond
formation
process.
Control
experiments
shed
some
light
on
catalyst/substrate
catalyst/catalyst
interactions
in
this
dual
catalytic
system
rationalize
related
kinetic/dynamic
kinetic
resolution
process
different
catalyst
combinations.
enantioenriched
γ-butyrolactone
products
were
converted
into
an
array
structurally
complex
molecules
organocatalysts
that
otherwise
inaccessible.
Chemical Reviews,
Journal Year:
2018,
Volume and Issue:
119(3), P. 1855 - 1969
Published: Dec. 24, 2018
In
this
review,
we
summarize
the
origin
and
advancements
of
iridium-catalyzed
asymmetric
allylic
substitution
reactions
during
past
two
decades.
Since
first
report
in
1997,
Ir-catalyzed
have
attracted
intense
attention
due
to
their
exceptionally
high
regio-
enantioselectivities.
been
significantly
developed
recent
years
many
respects,
including
ligand
development,
mechanistic
understanding,
substrate
scope,
application
synthesis
complex
functional
molecules.
an
explicit
outline
ligands,
mechanism,
scope
nucleophiles,
applications
is
presented.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(16), P. 5627 - 5639
Published: April 6, 2017
This
Perspective
presents
an
overview
of
catalytic
enantioselective
transformations
that
allow
convenient
access
to
all
stereoisomers
a
given
product
with
multiple
stereogenic
centers.
Particular
focus
is
placed
on
discussion
the
concept
stereodivergent
dual
catalysis
and
its
application
in
target-oriented
synthesis.
The
potential
this
development
new
as
well
implications
for
achieving
stereochemical
diversity
library
design
diversity-oriented
synthesis
are
also
discussed.
Chemical Reviews,
Journal Year:
2018,
Volume and Issue:
118(10), P. 5080 - 5200
Published: April 20, 2018
This
review
covers
diastereo-
and
enantiodivergent
catalyzed
reactions
in
acyclic
cyclic
systems
using
metal
complexes
or
organocatalysts.
Among
them,
nucleophilic
addition
to
carbon–carbon
carbon–nitrogen
double
bonds,
α-functionalization
of
carbonyl
compounds,
allylic
substitutions,
ring
opening
oxiranes
aziridines
are
considered.
The
diastereodivergent
synthesis
alkenes
from
alkynes
is
also
included.
Finally,
stereodivergent
intramolecular
intermolecular
cycloadditions
other
cyclizations
reported.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(4), P. 1508 - 1513
Published: Jan. 5, 2018
Cu/Ir
dual
catalysis
has
been
developed
for
the
stereodivergent
α-allylation
of
aldimine
esters.
The
method
enables
preparation
a
series
nonproteinogenic
α-amino
acids
(α-AAs)
bearing
two
contiguous
stereogenic
centers
in
high
yield
with
excellent
stereoselectivity.
All
four
product
stereoisomers
could
be
obtained
from
same
set
starting
materials
via
pairwise
combination
chiral
catalysts.
Notably,
one-pot
protocol
successfully
applied
bimetallic
complexes
to
simplify
manipulation
catalysis.
This
further
utilized
construction
key
intermediate
bioactive
pyrrolidine
derivative
and
concise
synthesis
plant
growth
regulator
(2S,3S)-2-amino-3-cyclopropylbutanoic
acid.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(6), P. 2080 - 2084
Published: Jan. 30, 2018
We
describe
a
fully
stereodivergent
synthesis
of
range
α,α-disubstituted
α-amino
acids
via
an
Ir/Cu-catalyzed
α-allylation
readily
available
imine
esters.
The
introduction
Cu-Phox
complex-activated
ester
into
the
chiral
iridium-catalyzed
allylic
allylation
process
is
crucial
for
its
high
reactivity
and
excellent
enantio-
diastereoselectivity
(up
to
>99%
ee
>20:1
dr).
Importantly,
two
catalysts
allow
full
control
over
configuration
stereocenters,
affording
all
stereoisomers
desired
products.
utility
this
methodology
was
demonstrated
by
synthesizing
dipeptides
analogues
bioactive
molecules
in
manner.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(24), P. 13382 - 13433
Published: Nov. 29, 2020
Synergistic
catalysis,
a
type
of
plural
catalysis
which
utilizes
at
least
two
different
catalysts
to
enable
reaction
between
separately
activated
substrates,
has
unlocked
plethora
previously
unattainable
transformations
and
novel
chemical
reactivity.
Despite
the
appreciable
utility
synergistic
specific
examples
involving
transition
metals
have
been
limited,
as
ensuring
judicious
choice
parameters
prevent
deactivation
catalysts,
undesirable
monocatalytic
event(s)
leading
side
products,
or
premature
termination
other
potentially
troublesome
outcomes
present
formidable
challenge.
Excluding
those
driven
by
photocatalytic
mechanisms,
this
review
will
highlight
reported
reactions
that
make
use
simultaneous
catalytic
cycles
metal
catalysts.
Journal of the American Chemical Society,
Journal Year:
2016,
Volume and Issue:
139(1), P. 87 - 90
Published: Dec. 17, 2016
The
preparation
of
all
possible
stereoisomers
a
given
chiral
molecule
bearing
multiple
stereocenters
by
simple
and
unified
method
is
significant
challenge
in
asymmetric
catalysis.
We
report
stereodivergent
allylic
substitutions
with
aryl
acetic
acid
esters
catalyzed
synergistically
metallacyclic
iridium
complex
benzotetramisole.
Through
permutations
the
enantiomers
two
catalysts,
four
products
adjacent
are
accessible
high
diastereoselectivity
enantioselectivity.
resulting
activated
ester
can
be
converted
readily
to
enantioenriched
amides,
unactivated
esters,
carboxylic
acids
one-pot
manner.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(31), P. 8942 - 8973
Published: April 13, 2017
Abstract
Recent
developments
of
stereoselective
biocatalytic
and
chemocatalytic
methods
are
discussed.
The
review
provides
a
guide
to
the
use
in
area
chemical
synthesis
with
focused
attention
on
retrosynthetic
considerations
analysis.
transformations
presented
organized
according
bond
disconnections
attendant
synthetic
methods.
is
expected
lead
better
understanding
characteristics
distinctions
two
complementary
approaches.
It
depicts
for
researchers
bio‐
chemocatalysis
road
map
challenges
opportunities
evolution
(and
at
times
revolution)
synthesis.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(3), P. 1029 - 1032
Published: Jan. 11, 2017
We
report
an
enantioselective
coupling
between
α-branched
aldehydes
and
alkynes
to
generate
vicinal
quaternary
tertiary
carbon
stereocenters.
The
choice
of
Rh
organocatalyst
combination
allows
for
access
all
possible
stereoisomers
with
high
enantio-,
diastereo-,
regioselectivity.
Our
study
highlights
the
power
catalysis
activate
two
common
functional
groups
provide
divergent
constitutional
structures.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(37), P. 14554 - 14559
Published: Sept. 3, 2019
Herein
we
describe
the
use
of
synergistic
Pd
and
Cu
catalysis
for
stereodivergent
coupling
reactions
between
1,3-dienes
aldimine
esters.
By
using
different
enantiomers
two
metal
catalysts,
all
four
stereoisomers
products,
which
have
vicinal
stereocenters,
could
be
accessed
with
high
diastereo-
enantioselectivity.
This
atom-economical
cross-coupling
reaction
has
a
wide
substrate
scope
good
functional
group
tolerance.
Our
work
highlights
power
asymmetric
involving
Pd-hydride
catalysts.
