Angewandte Chemie,
Год журнала:
2024,
Номер
136(44)
Опубликована: Авг. 6, 2024
Abstract
The
transition
metal‐catalyzed
asymmetric
hydro‐functionalization
of
1,3‐dienes
has
been
well
explored,
but
most
reactions
focus
on
electron‐neutral
substrates
in
an
intermolecular
manner.
Here
we
first
demonstrate
that
readily
available
2,4‐dienyl
hydrazones
and
oximes
can
be
efficiently
utilized
the
hydro‐cyclization
reaction
under
co‐catalysis
a
Brønsted
acid
chiral
palladium
complex,
furnishing
multifunctional
dihydropyrazones
dihydroisoxazoles,
respectively.
Diverse
substitution
patterns
for
both
types
electron‐deficient
diene
compounds
are
tolerated,
corresponding
heterocycles
were
generally
constructed
with
moderate
to
excellent
enantioselectivity,
which
elaborated
access
products
higher
molecular
complexity
diversity.
Control
experiments
density
functional
theory
calculations
support
α‐regioselective
protonation
dienyl
by
concurrent
π‐Lewis
base
activation
Pd
0
complex
is
energetically
favoured
formation
active
π‐allylpalladium
intermediates,
outer‐sphere
allylic
amination
or
etherification
mode
adopted
deliver
observed
cyclized
enantioselectively.
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8657 - 8739
Опубликована: Июль 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(10), С. 6422 - 6437
Опубликована: Март 1, 2024
The
development
of
a
new
catalytic
strategy
plays
vital
role
in
modern
organic
chemistry
since
it
permits
bond
formation
an
unprecedented
and
more
efficient
manner.
Although
the
application
preformed
metal
complexes
as
π-base-activated
reagents
have
enabled
diverse
transformations
elegantly,
concept
by
directly
utilizing
transition
metals
π-Lewis
base
catalysts
remain
underdeveloped,
especially
field
asymmetric
catalysis.
Here,
we
outline
our
perspective
on
discovery
palladium(0)
catalyst,
which
is
capable
increasing
highest
occupied
molecular
orbital
(HOMO)
energy
both
electron-neutral
electron-deficient
1,3-dienes
1,3-enynes
upon
flexible
η2-complexes
formed
situ
resultant
π-backdonation.
Thus,
fruitful
carbon–carbon-forming
reactions
with
electrophiles
can
be
achieved
enantioselectively
vinylogous
addition
pattern,
conceptually
different
from
classical
oxidative
cyclization
mechanism.
Emphasis
will
given
to
mechanism
elucidation,
features,
reaction
design
together
further
this
emerging
field.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(10), С. 6936 - 6946
Опубликована: Фев. 28, 2024
Here,
we
describe
a
cooperative
Pd(0)/chiral
phosphoric
acid
catalytic
system
that
allows
us
to
realize
the
first
chemo-,
regio-,
and
enantioselective
sequential
cross-[4
+
2]-cycloaddition/decarboxylation
reaction
between
2-pyrones
unactivated
acyclic
1,3-dienes.
The
key
success
of
this
transformation
is
utilization
an
achiral
N-heterocyclic
carbene
(NHC)
as
ligand
newly
developed
chiral
cocatalyst.
Experimental
investigations
computational
studies
support
idea
Pd(0)/NHC
complex
acts
π-Lewis
base
increase
nucleophilicity
1,3-dienes
via
η2
coordination,
while
simultaneously
increases
electrophilicity
by
hydrogen
bonding.
By
synergistic
catalysis,
2]-cycloaddition
decarboxylation
proceeds
efficiently,
enabling
preparation
wide
range
vinyl-substituted
1,3-cyclohexadienes
in
good
yields
enantioselectivities.
synthetic
utility
demonstrated
transformations
product
various
valuable
six-membered
carbocycles.
Organic Process Research & Development,
Год журнала:
2024,
Номер
28(4), С. 949 - 977
Опубликована: Апрель 8, 2024
P-Chiral
phosphorus
ligands
received
little
attention
in
organic
chemistry
until
Knowles
made
his
landmark
contribution
asymmetric
hydrogenation
by
developing
the
P-chiral
CAMP
and
DIPAMP.
The
development
of
accelerated
end
last
century
with
advent
some
highly
efficient
renowned
for
hydrogenation,
including
BisP*,
TangPhos,
QuinoxP*,
DuanPhos,
et
al.
However,
most
reported
were
air-sensitive,
difficult
to
make,
or
lacked
structural
modularity,
hampering
their
availability
applicability.
sterically
electronically
tunable
is
particularly
desirable.
Over
past
decade,
a
family
hindered,
electron-rich,
structurally
tunable,
air-stable
dihydrobenzooxaphosphole
emerged
that
proved
be
versatile
various
transformations.
5
years
witnessed
an
increasing
number
studies
related
these
discovery
unprecedented
catalytic
properties
This
review
highlights
unique
catalysis
applications
synthesis
natural
products
therapeutic
agents.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(5), С. 3413 - 3418
Опубликована: Фев. 20, 2024
An
efficient
cascade
intramolecular
cyclization/intermolecular
nucleophilic
addition
reaction
of
allenyl
benzoxazinone
with
isatin
or
isatin-derived
ketimine
has
been
established
by
using
Pd0-π-Lewis
base
catalysis.
A
series
3-hydroxy-2-oxindoles
and
3-amino-2-oxindoles
quaternary
carbon
atoms
at
the
C3
position
were
synthesized
in
good
yields
under
mild
conditions
through
this
protocol.
Organic Letters,
Год журнала:
2024,
Номер
26(7), С. 1483 - 1488
Опубликована: Фев. 12, 2024
Presented
herein
is
a
palladium-catalyzed
asymmetric
(3
+
2)
annulation
reaction
between
1,3-dienes
and
2-formylarylboronic
acids,
proceeding
in
cascade
vinylogous
addition
Suzuki
coupling
process.
Both
electron-neutral
electron-deficient
are
compatible
under
similar
catalytic
conditions,
distinct
regioselectivity
observed
via
functional-group
control
of
1,3-diene
substrates.
A
collection
1-indanols
with
dense
functionalities
constructed
stereoselectively.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(44)
Опубликована: Авг. 6, 2024
Abstract
The
transition
metal‐catalyzed
asymmetric
hydro‐functionalization
of
1,3‐dienes
has
been
well
explored,
but
most
reactions
focus
on
electron‐neutral
substrates
in
an
intermolecular
manner.
Here
we
first
demonstrate
that
readily
available
2,4‐dienyl
hydrazones
and
oximes
can
be
efficiently
utilized
the
hydro‐cyclization
reaction
under
co‐catalysis
a
Brønsted
acid
chiral
palladium
complex,
furnishing
multifunctional
dihydropyrazones
dihydroisoxazoles,
respectively.
Diverse
substitution
patterns
for
both
types
electron‐deficient
diene
compounds
are
tolerated,
corresponding
heterocycles
were
generally
constructed
with
moderate
to
excellent
enantioselectivity,
which
elaborated
access
products
higher
molecular
complexity
diversity.
Control
experiments
density
functional
theory
calculations
support
α‐regioselective
protonation
dienyl
by
concurrent
π‐Lewis
base
activation
Pd
0
complex
is
energetically
favoured
formation
active
π‐allylpalladium
intermediates,
outer‐sphere
allylic
amination
or
etherification
mode
adopted
deliver
observed
cyclized
enantioselectively.
Green Chemistry,
Год журнала:
2023,
Номер
25(14), С. 5692 - 5697
Опубликована: Янв. 1, 2023
The
first
regio-reversed
domino
processes
of
triketone
enones
with
azlactones
are
established
leading
to
the
formation
a
variety
bicyclic
furofurans
bearing
vicinal
quaternary
carbons
in
good
excellent
yields.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(14), С. 3900 - 3905
Опубликована: Янв. 1, 2024
A
multi-catalytic
system
combining
gold,
palladium
and
phosphoric
acid
was
applied
for
asymmetric
assembly
of
ynamides
carbonate
4-hydroxy-2-cyclopentenone,
furnishing
furo[2,3-
b
]pyridines
in
high
yields
stereoselectivities.
