European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
26(1)
Опубликована: Дек. 9, 2022
Abstract
Dual
catalysis
is
one
of
the
most
powerful
strategies
for
development
chemical
reactions
in
organic
synthesis.
This
strategy
can
be
divided
into
cooperative
catalysis,
relay
and
sequential
according
to
actual
mode
operation
communication
between
catalysts.
In
recent
years,
such
has
been
applied
a
large
number
studies
since
it
advantages
of:
1)
increasing
reactivity
enabling
challenging
transformations;
2)
offering
way
controlling
stereoselectivity
asymmetric
reactions,
which
traditional
catalytic
systems;
3)
catalyze
stereodivergent
synthesis
molecules
bearing
or
more
stereocenters
from
same
starting
materials.
Perspective,
intends
introduce
reader
EurJOC
special
collection
on
Catalysis
,
aims
summarize
different
categories
dual
demonstrate
their
benefits
constructing
new
bonds
selective
manner.
Finally,
current
challenges
trends
will
also
presented.
Chemical Reviews,
Год журнала:
2021,
Номер
121(8), С. 4373 - 4505
Опубликована: Март 19, 2021
This
Review
compiles
the
evolution,
mechanistic
understanding,
and
more
recent
advances
in
enantioselective
Pd-catalyzed
allylic
substitution
decarboxylative
oxidative
substitutions.
For
each
reaction,
catalytic
data,
as
well
examples
of
their
application
to
synthesis
complex
molecules,
are
collected.
Sections
which
we
discuss
key
aspects
for
high
selectivity
a
comparison
with
other
metals
(with
advantages
disadvantages)
also
included.
asymmetric
substitution,
data
grouped
according
type
nucleophile
employed.
Because
prominent
position
use
stabilized
carbon
nucleophiles
heteronucleophiles,
many
chiral
ligands
have
been
developed.
To
better
compare
results,
they
presented
by
ligand
types.
reactions
mainly
promoted
PHOX
or
Trost
ligands,
justifies
organizing
this
section
chronological
order.
results
used.
ACS Catalysis,
Год журнала:
2021,
Номер
11(7), С. 3891 - 3915
Опубликована: Март 15, 2021
Multicatalysis
is
an
emerging
field
targeting
the
development
of
efficient
catalytic
transformations
to
quickly
convert
relatively
simple
starting
materials
into
more
complex
value-added
products.
Within
multicatalytic
processes
either
multiple
catalysts
execute
single
reactions
or
precise
sequences
occur
in
a
"one-pot"
fashion.
Attractively,
protocols
not
only
enable
that
are
inaccessible
through
classic
approaches
but
also
able
significantly
reduce
time,
waste,
and
cost
synthetic
processes,
making
organic
synthesis
resources
efficient.
In
this
Perspective
article,
we
review
different
strategies
multicatalysis
bring
distinct
challenges
opportunities.
We
divide
overarching
three
main
categories:
cooperative,
domino,
relay
catalysis.
Each
category
described
along
with
representative
examples
highlight
its
features.
Special
emphasis
dedicated
catalysis,
which
further
discussed
subcategories.
Lastly,
provide
analysis
systems
incorporate
higher
levels
complexity
underscore
potential
systems.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(19), С. 7285 - 7291
Опубликована: Май 10, 2021
Herein
we
describe
a
protocol
for
the
unprecedented
stereodivergent
synthesis
of
tertiary
fluoride-tethered
allenes
bearing
stereogenic
center
and
axis
via
Cu/Pd
synergistic
catalysis.
A
broad
scope
conjugated
enynes
are
coupled
with
various
α-fluoroesters
in
high
yields
diastereoselectivities
generally
>99%
ee.
In
addition,
four
stereoisomers
allene
products
ensure
precise
access
to
corresponding
fluorinated
hydrofurans
novel
axial-to-central
chirality
transfer
process.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(32), С. 12622 - 12632
Опубликована: Авг. 5, 2021
In
contrast
to
the
widely
explored
methods
for
asymmetric
synthesis
of
molecules
bearing
a
single
stereocenter
or
adjacent
stereocenters,
concurrent
construction
1,3-stereogenic
centers
in
an
enantio-
and
diastereoselective
manner
remains
challenge,
especially
acyclic
systems.
Herein,
we
report
diastereodivergent
1,3-nonadjacent
stereocenters
allenyl
axial
central
chirality
through
synergistic
Pd/Cu-catalyzed
dynamic
kinetic
allenylation
with
racemic
allenylic
esters.
The
protocol
is
suitable
wide
range
substrates
including
challenging
esters
less
sterically
bulky
substituents
provided
chiral
products
high
levels
diastereoselectivities
(up
>20:1
dr
>99%
ee).
Furthermore,
several
representative
transformations
involving
axial-to-central
transfer
were
conducted,
affording
useful
structural
motifs
containing
nonadjacent
manner.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(45)
Опубликована: Авг. 2, 2022
Abstract
Bimetallic
catalysis
has
emerged
as
an
efficient
strategy
for
the
development
of
new
chemical
reactions.
Importantly,
this
also
provides
a
simple
and
powerful
platform
stereodivergent
synthesis,
whereby
all
possible
stereoisomers
products
bearing
two
stereocenters
can
be
easily
prepared
from
same
set
starting
materials.
In
Minireview,
allylic
substitution,
propargylic
hydrofunctionalization,
annulation
based
on
bimetallic
been
summarized.
It
is
expected
that
more
catalytic
systems
will
developed
applied
synthesis
valuable
molecules.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(47), С. 24941 - 24949
Опубликована: Сен. 17, 2021
The
development
of
efficient
and
straightforward
methods
for
obtaining
all
optically
active
isomers
structurally
rigid
spirocycles
from
readily
available
starting
materials
is
great
value
in
drug
discovery
chiral
ligand
development.
However,
the
stereodivergent
synthesis
bearing
multiple
stereocenters
remains
an
unsolved
challenge
owing
to
steric
hindrance
ring
strain.
Herein,
we
report
enantio-
diastereodivergent
through
dual-metal-catalyzed
[3+2]
annulation
oxy
π-allyl
metallic
dipoles
with
less
commonly
employed
nucleophilic
(imino
esters).
A
series
spiro
compounds
a
pyrroline
olefin
were
easily
synthesized
manner
(up
19:1
dr,
>99
%
ee),
which
showed
promise
as
new
type
N-olefin
ligand.
Preliminary
mechanistic
studies
also
carried
out
understand
process
this
bimetallic
catalysis.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(29), С. 10948 - 10962
Опубликована: Июль 15, 2021
Metal-hydride-catalyzed
hydroalkylation
of
1,3-dienes
with
enolizable
carbonyl
compounds
is
an
atom-
and
step-economical
method
for
preparing
chiral
molecules
allylic
stereocenters.
Although
high
diastereo-
enantioselectivities
have
been
achieved
many
coupling
partners,
aldehydes
not
yet
used
this
purpose
because
they
are
less
stable
than
other
under
basic
conditions
the
potential
to
rapidly
epimerize
at
α-position.
Moreover,
stereodivergent
reactions
access
complementary
diastereomers
vicinal
stereocenters
challenging.
Herein,
we
describe
a
synergistic
palladium/amine
catalyst
system
that
allowed
us
achieve
first
aldehydes.
By
choosing
appropriate
combination
palladium
amine
catalysts,
could
obtain
either
syn
or
anti
products,
therefore
provides
highly
enantioselective
α,β-vicinal
Density
functional
theory
calculations
revealed
mechanism
involving
PdH
formation
migratory
insertion
into
alkene,
followed
by
C–C
bond
formation.
The
origin
stereoselectivities
was
investigated
means
distortion/interaction
analysis.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(47), С. 24930 - 24940
Опубликована: Окт. 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.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(4), С. 1971 - 1985
Опубликована: Янв. 20, 2022
Comprehensive
computational
studies
were
carried
out
to
explore
the
mechanisms
of
enantioselective
Cu/Pd
and
stereodivergent
Cu/Ir
dual-catalytic
syntheses
α,α-disubstituted
α-amino
acids
(α-AAs).
A
chiral
copper
azomethine
ylide
undergoes
facile
α-allylation
with
racemic
π-allylpalladium
species
or
stereopure
π-allyliridium
complex
stereoconvergently
stereodivergently
furnish
single/double
stereocenters,
respectively.
Stereoselectivity
at
α-center
is
controlled
by
facial
selectivity
respect
prochiral
nucleophile.
Despite
apparently
similar
transition-state
assemblies,
models
distortion/interaction
analyses
disclose
versatile
modes
stereoinduction
wherein
can
face-selectively
intercept
metal−π-allyl
intermediates
utilizing
attractive
dispersion
interactions
and/or
sterically
caused
distortions.
Generation
β-stereocenter
in
system
relies
on
a
stereospecifically
generated
allyliridium
electronically
branched-to-linear
selectivity,
while
dual
yields
linear
monochiral
product
due
steric
factors
π–π
stacking
interactions.
The
demonstrate
molecular
level
how
ligand-encoded
information
transferred
α-/β-sites
resulting
α-AAs
mode
regio-/stereoselection
altered
differences
transition-metal-stabilized
coupling
partners.
To
facilitate
stereoselective
catalysis,
suite
analytical
tools
extract
controlling
for
asymmetric
induction
demonstrated.