Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(48)
Published: Sept. 30, 2022
Abstract
An
iridium‐catalyzed
asymmetric
allylic
benzylation
of
aryl
vinyl
carbinols
under
light
irradiation
is
described.
2‐Methylbenzophenone
derivatives
are
employed
and
activated
to
hydroxy‐
o
‐quinodimethanes
by
an
ultraviolet
(UV)
light.
This
approach
enables
with
high
enantioselectivity
(up
99
%
ee)
from
readily
available
2‐methylbenzophenones
without
the
utilization
strong
bases,
pre‐activation
or
pre‐functionalization
substrates.
Moreover,
deuterium
experiments
reveal
generation
nucleophilic
benzyl
species
2‐methylbenzophenone
UV
irradiation.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(22), P. 9564 - 9569
Published: May 27, 2022
Here
we
report
an
asymmetric
formal
nucleophilic
o-cresolylation
reaction
with
the
Morita-Baylis-Hillman
(MBH)
carbonates
from
2-cyclohexanones
and
diverse
aldehydes
under
palladium
catalysis,
by
in
situ
generation
of
electron-neutral
HOMO-raised
η2-Pd(0)-dienone
complexes
via
oxidative
insertion/π-σ-isomerization/β-H
elimination
activation
sequence.
The
subsequent
umpolung
vinylogous
addition
to
a
variety
imines
is
realized
upon
Pd(0)-mediated
π-Lewis
base
finally
furnishing
o-cresolylated
products
followed
another
cascade
π-σ-isomerization/β-H
elimination/aromatization
process.
Moderate
excellent
diastereo-
enantioselectivity
are
achieved
for
substantial
substrate
assemblies
employing
newly
designed
bulky
chiral
phosphonamidite
ligand,
resultant
multifunctional
can
be
facilely
elaborated
access
enantioenriched
architectures.
In
addition,
catalytic
pathway
finely
illuminated
control
experiments.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(20)
Published: March 3, 2022
Abstract
Herein,
an
Ir‐catalyzed
asymmetric
allylic
substitution
reaction
of
methyl
azaarenes
is
described.
Azaarenes
such
as
(benzo)thiazole,
oxazole,
benzoimidazole,
pyridine,
and
(iso)quinoline
are
all
tolerated.
The
corresponding
chiral
azaarene
derivatives
obtained
in
good
yields
with
high
enantioselectivity
(up
to
96
%
yield
99
ee).
utilization
the
Knochel
reagent
TMPZnBr⋅LiBr
warrants
situ
formation
benzylic
nucleophiles
without
additional
activating
reagents.
1
H
NMR
studies
suggested
a
two‐fold
function
this
reaction.
synthetic
utility
method
has
been
showcased
by
concise
enantioselective
synthesis
allosteric
protein
kinase
modulator.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(48)
Published: Sept. 30, 2022
Abstract
An
iridium‐catalyzed
asymmetric
allylic
benzylation
of
aryl
vinyl
carbinols
under
light
irradiation
is
described.
2‐Methylbenzophenone
derivatives
are
employed
and
activated
to
hydroxy‐
o
‐quinodimethanes
by
an
ultraviolet
(UV)
light.
This
approach
enables
with
high
enantioselectivity
(up
99
%
ee)
from
readily
available
2‐methylbenzophenones
without
the
utilization
strong
bases,
pre‐activation
or
pre‐functionalization
substrates.
Moreover,
deuterium
experiments
reveal
generation
nucleophilic
benzyl
species
2‐methylbenzophenone
UV
irradiation.
Chinese Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
42(10), P. 3240 - 3240
Published: Jan. 1, 2022
Epoxides
and
aziridines
are
important
three-membered
cyclic
compounds,
which
exhibit
high
reactivity
due
to
their
strong
strain
in
molecules.The
asymmetric
ring-opening
reactions
of
epoxides
catalyzed
by
transition
metals
efficient
strategies
for
the
construction
chiral
molecules
containing
O/N
atoms.In
this
way,
a
series
alcohols,
amines
heterocycles
can
be
constructed.The
recent
progress
metal-catalyzed
past
two
decades
is
reviewed
with
emphasis
on
influence
kinds
metal
catalysts,
nucleophiles,
ligands.Furthermore,
possible
reaction
mechanisms
applications
discussed,
future
development
field
also
prospected.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(27), P. 4987 - 4991
Published: July 1, 2022
An
enantio-
and
regioconvergent
nickel-catalyzed
benzylation
of
racemic
silylated
allylic
electrophiles
with
benzylzinc
nucleophiles
is
reported.
The
key
feature
this
method
that
the
homocoupling
pathways
both
nucleophile
electrophile
are
minimized.
A
diverse
set
electronically
modified
reagents
was
tolerated.
vinylsilane
products
stereocenters
were
formed
in
moderate
to
high
yields
enantioselectivities.
regioconvergence
result
steering
effect
silyl
group.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(20)
Published: March 3, 2022
Abstract
Herein,
an
Ir‐catalyzed
asymmetric
allylic
substitution
reaction
of
methyl
azaarenes
is
described.
Azaarenes
such
as
(benzo)thiazole,
oxazole,
benzoimidazole,
pyridine,
and
(iso)quinoline
are
all
tolerated.
The
corresponding
chiral
azaarene
derivatives
obtained
in
good
yields
with
high
enantioselectivity
(up
to
96
%
yield
99
ee).
utilization
the
Knochel
reagent
TMPZnBr⋅LiBr
warrants
situ
formation
benzylic
nucleophiles
without
additional
activating
reagents.
1
H
NMR
studies
suggested
a
two‐fold
function
this
reaction.
synthetic
utility
method
has
been
showcased
by
concise
enantioselective
synthesis
allosteric
protein
kinase
modulator.
