Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(14), P. 4002 - 4005
Published: March 7, 2017
Abstract
An
enantioselective
iridium‐catalyzed
allylic
substitution
with
a
set
of
highly
unstabilized
nucleophiles
generated
in
situ
from
2‐methylpyridines
is
described.
Enantioenriched
2‐substituted
pyridines,
which
are
frequently
encountered
natural
products
and
pharmaceuticals,
could
be
easily
constructed
by
this
simple
method
good
yields
excellent
enantioselectivity.
The
synthetic
utility
the
pyridine
demonstrated
through
synthesis
key
intermediate
reported
Na
+
/H
exchanger
inhibitor
total
(−)‐lycopladine
A.
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:
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.
Organic & Biomolecular Chemistry,
Journal Year:
2017,
Volume and Issue:
15(17), P. 3550 - 3567
Published: Jan. 1, 2017
Numerous
efficient
synthetic
methods
for
enantioselective
indole
functionalizations
have
emerged
in
recent
years.
This
review
summarizes
the
major
achievements
transition-metal-catalyzed
functionalization
reactions
since
2010
and
focuses
on
C-C
bond
formation
processes,
including
alkylations,
arylations,
cycloaddition
reactions,
other
reactions.
It
intends
to
give
a
compendious
overview
of
significant
progress
achieved
this
area.
ACS Catalysis,
Journal Year:
2016,
Volume and Issue:
6(8), P. 4814 - 4858
Published: June 9, 2016
Chiral
monophosphorus
ligands
are
playing
an
important
role
for
the
recent
advances
in
asymmetric
catalysis.
This
review
summarizes
latest
progress
various
catalytic
reactions
with
employment
of
chiral
including
allylic
substitution,
dearomative
arylation,
Heck
reaction,
cross-coupling,
C–H
bond
functionalization,
coupling
π
systems,
addition,
hydrogenation,
and
organocatalytic
reactions.
The
new
reactivity,
selectivity,
reaction
mechanism
enabled
by
these
discussed.
Chemistry - A European Journal,
Journal Year:
2016,
Volume and Issue:
22(34), P. 11918 - 11933
Published: July 5, 2016
Abstract
Recent
advances
in
dearomatization
through
halofunctionalization
reactions
are
summarized
this
Minireview.
Two
general
categories
of
strategies
currently
employed
field.
On
one
hand,
the
reaction
can
be
initiated
with
electrophilic
halogenation
at
an
alkyne
or
alkene
moiety.
The
resulting
halonium
ion
intermediate
is
then
captured
by
a
pendant
aromatic
ring
ipso
position,
affording
product.
other
directly
take
place
substituted
arene,
and
final
product
furnished
deprotonation
intramolecular
nucleophilic
trap.
Highly
enantioselective
variants
have
been
realized
latter
case
organocatalysis
transition
metal
catalysis.
By
applying
these
methods,
various
valuable
halogenated
polycyclic
molecular
architectures
obtained
from
readily
available
starting
materials.
Journal of the American Chemical Society,
Journal Year:
2016,
Volume and Issue:
138(18), P. 5793 - 5796
Published: April 19, 2016
Asymmetric
synthesis
of
indole-annulated
medium-sized-ring
compounds
is
developed
through
an
iridium-catalyzed
allylic
dearomatization/retro-Mannich/hydrolysis
cascade
reaction.
The
reaction
features
mild
conditions
and
a
broad
substrate
scope.
Under
the
optimal
conditions,
various
seven-,
eight-,
or
nine-membered-ring
can
be
afforded
in
good
to
excellent
yields
enantioselectivity.
proposed
mechanism
supported
by
capturing
dearomatized
intermediate
situ
reduction.
Angewandte Chemie International Edition,
Journal Year:
2016,
Volume and Issue:
55(12), P. 4044 - 4048
Published: Feb. 17, 2016
Abstract
The
first
enantioselective
total
synthesis
of
(−)‐aspidophylline
A,
including
assignment
its
absolute
configuration
has
been
accomplished.
A
key
element
the
is
a
highly
indole
allylic
alkylation/iminium
cyclization
cascade
which
was
developed
by
employing
combination
Lewis
acid
activation
and
an
iridium/ligand
catalyst.
This
strategy
relies
on
direct
use
2,3‐disubstituted
indoles
with
secondary
alcohols
appended
at
C2
heteronucleophiles
C3,
are
easily
prepared
from
simple
starting
materials
under
C−H
conditions.
Angewandte Chemie International Edition,
Journal Year:
2016,
Volume and Issue:
55(10), P. 3496 - 3499
Published: Feb. 5, 2016
Abstract
An
iridium‐catalyzed
intramolecular
asymmetric
allylic
dearomatization
reaction
of
naphthol
derivatives
is
described.
Challenges
confronted
in
this
include
chemoselectivity
between
carbon
and
oxygen
atoms
as
nucleophilic
centers,
diastereoselectivity
when
contiguous
chiral
centers
are
generated,
enantioselective
control
for
constructing
an
all‐carbon
quaternary
stereocenter.
In
the
presence
iridium
catalyst
generated
from
[{Ir(dbcot)Cl}
2
]
(dbcot=dibenzocyclooctatetraene)
a
new
THQphos
(tetrahydroquinolinedinaphthophosphoramidite)
ligand,
various
spironaphthalenones
were
obtained
with
up
to
greater
than
95:5
C/O
selectivity,
d.r.,
99
%
ee
,
thus
providing
general
method
naphthols.
