Organic Letters,
Journal Year:
2019,
Volume and Issue:
22(1), P. 164 - 167
Published: Dec. 23, 2019
A
straight
synthetic
approach
to
fused
polycyclic
tropane
scaffold
formation
through
an
asymmetric
dearomatization
cycloaddition
process
of
2-nitrobenzofurans
with
cyclic
azomethine
ylides
was
successfully
developed.
In
the
presence
a
chiral
copper
complex,
derived
from
Cu(OAc)2
and
diphosphine
ligand,
series
derivatives
were
obtained
in
high
yields
(75–91%)
excellent
enantioselectivities
(90–98%).
The
utility
this
method
showcased
by
facile
transformation
product.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(8), P. 4373 - 4505
Published: March 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.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(1), P. 227 - 263
Published: May 29, 2020
This
review
describes
the
development
of
enantioselective
methods
for
ring
opening
cyclopropanes.
Both
approaches
based
on
reaction
nonchiral
cyclopropanes
and
(dynamic)
kinetic
resolutions
asymmetric
transformations
chiral
substrates
are
presented.
The
is
organized
according
to
substrate
classes,
starting
by
more
mature
field
donor-acceptor
Emerging
acceptor-
or
donor-only
then
last
part
reactive
three-membered
rings
substituted
with
unsaturations
a
particular
focus
vinylcyclopropanes,
alkylidenecyclopropanes,
vinylidenecyclopropanes.
In
two
decades,
has
grown
from
proof
concept
stage
broad
range
accessing
enantioenriched
building
blocks,
further
extensive
developments
can
be
expected
in
future.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(1), P. 110 - 139
Published: Aug. 6, 2020
In
this
review,
transition
metal-catalyzed
methodologies
and
applications
that
exploit
C–C
bond
cleavage
of
vinylcyclopropanes
(VCPs)
are
summarized
with
a
focus
on
cycloaddition
related
addition
reactions.
Transition
metals,
including
palladium,
nickel,
iron,
ruthenium,
rhodium,
cobalt,
iridium,
can
catalyze
the
bonds
in
activated
or
nonactivated
VCPs.
Additionally,
these
bond-breaking
reactions
occur
as
intra-
intermolecular
processes.
The
properties
VCPs
discussed
Introduction.
Various
involving
then
next
chapter.
cycloadditions
following
Finally,
challenges
potential
opportunities
outlined
last
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(41), P. 14653 - 14659
Published: Aug. 17, 2019
Abstract
A
highly
enantioselective
dicarbofunctionalization
of
unactivated
alkenes
was
implemented
by
a
Pd‐catalyzed
asymmetric
tandem
Heck/Suzuki
coupling
reaction.
This
reaction
represents
the
first
example
intramolecular
cyclization/cross‐coupling
olefin‐tethered
aryl
halides
with
alkyl‐,
alkenyl‐
or
arylboronic
acids,
and
provides
rapid
access
to
number
chiral
compounds,
such
as
dihydrobenzofurans,
indolines,
chromanes,
indanes
bearing
quaternary
stereocenter,
in
good
yields
excellent
enantioselectivities.
The
practicality
this
validated
modification
biologically
complex
molecules
peptides,
piperitol,
CB2
receptor
agonists,
etc.
Moreover,
synthesis
two
enantiomers
can
be
easily
realized
simple
change
order
steps
sequence.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(11), P. 2723 - 2739
Published: April 7, 2021
Abstract
Indole
is
one
of
the
most
important
heterocycles
in
organic
synthesis,
natural
products,
and
drug
discovery.
Recently,
tremendous
advances
selective
functionalization
indoles
have
been
reported.
Although
powered
by
transition
metal
catalysis,
exceedingly
useful
methods
absence
metals
also
In
this
review,
we
provide
an
overview
reactions
that
published
last
years
with
a
focus
on
recent
advances,
aims,
future
trends.
The
review
organized
positional
selectivity
type
used
for
functionalization.
particular,
discuss
major
transition‐metal‐catalyzed
C−H
at
classical
C2/C3
positions,
remote
C4/C7
cross‐coupling,
transition‐metal‐free
magnified
image
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(7), P. 1955 - 1959
Published: Dec. 18, 2018
The
kinetics
of
(3+2)
cycloaddition
reactions
18
different
donor-acceptor
cyclopropanes
with
the
same
aldehyde
were
studied
by
in
situ
NMR
spectroscopy.
Increasing
electron
density
donor
residue
accelerates
reaction
a
factor
up
to
50
compared
standard
system
(donor
group=phenyl),
whereas
electron-withdrawing
substituents
slow
down
660.
This
behavior
is
agreement
Hammett
substituent
parameter
σ.
obtained
rate
constants
from
cycloadditions
correlate
well
data
additionally
(3+n)
nitrone
(n=3)
and
an
isobenzofuran
(n=4).
A
comparison
kinetic
bond
lengths
cyclopropane
(obtained
X-ray
diffraction
computation),
or
1
H
13
C
shifts,
revealed
no
correlation.
However,
computed
relaxed
force
proved
be
good
indicator
for
reactivity
three-membered
ring.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(7), P. 2769 - 2775
Published: Nov. 22, 2019
Abstract
Sonogashira‐type
cross‐couplings
are
one
of
the
most
significant
alkynylations
in
organic
chemistry.
One
first
palladium‐catalyzed
intramolecular
Heck/Sonogashira
reactions
alkenes
with
terminal
alkynes
is
now
reported.
With
this
method,
a
variety
uniquely
substituted
chiral
benzene‐fused
heterocycles
bearing
propargyl‐substituted
all‐carbon
quaternary
stereocenter
were
obtained
straightforward,
high‐yielding,
and
highly
stereoselective
manner
under
mild
conditions.
Salient
features
process
include
use
readily
available
substrates,
high
selectivities,
broad
substrate
scope
as
well
versatile
product
functionalizations.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(17), P. 5739 - 5743
Published: Feb. 27, 2019
Abstract
Dearomatization
of
anthranils
with
vinylcyclopropanes
(VCPs)
by
Pd‐catalyzed
[4+3]
cyclization
reaction
has
been
realized.
In
the
presence
a
catalytic
amount
borane
as
an
activator,
bridged
cyclic
products
were
obtained
in
good
to
excellent
yields
stereoselectivities.
By
introducing
chiral
PHOX
ligand
(
L5
),
asymmetric
dearomatization
reactions
proceeded
enantioselectivity.
Borane
plays
key
role
for
reactivity,
likely
owing
formation
borane–anthranil
complex
which
confirmed
NMR
experiments.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(3), P. 1340 - 1345
Published: Sept. 10, 2019
Abstract
Chiral
sulfones
are
of
great
importance
in
medicinal
chemistry
and
chemical
synthesis.
Efficient
methods
for
preparing
enantiomerically
enriched
sulfone‐containing
molecules
can
therefore
be
significant
value;
such
methods,
however,
uncommon.
Herein,
we
report
the
first
general
palladium‐catalyzed
sulfonylation
vinyl
cyclic
carbonates
with
sodium
sulfinates.
A
series
tertiary
allylic
were
synthesized
good
yields
excellent
enantiomeric
ratios.
Both
aliphatic‐
aryl‐substituted
suitable
reactants
results.
This
reaction
features
broad
substrates
scope,
readily
available
starting
materials,
regio‐
enantioselectivity,
synthesis
sulfone‐bearing
quaternary
carbon
stereocenters.
Through
geranyl
derived
carbonate
1
h
,
achieve
formal
total
(+)‐agelasidine
A.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(41), P. 13242 - 13252
Published: Sept. 21, 2018
A
three-component
coupling
using
lithiated
indoles,
boronate
esters
and
allylic
acetates
generates
chiral
indolines
with
adjacent
quaternary
stereocenters.
Successful
stereocontrol
required
the
use
of
phosphoramidite
ligands
not
previously
described
for
organopalladium
chemistry.
Mechanistic
studies
indicate
a
monodentate
PdL
intermediate,
stepwise
allylation-aryl/alkyl
migration.
protodeborylation
strategy
was
used
to
install
C–H
bond
in
place
C–B
bond.
photoredox
replace
C–C
highly
diastereoselective
manner.
In
specific
case
methyl-vinyl
ketone,
novel
radical-mediated
annulation
provides
polycyclic
products
high
enantio-
diastereoselectivity.
