Journal of the American Chemical Society,
Год журнала:
2015,
Номер
137(30), С. 9716 - 9721
Опубликована: Июль 5, 2015
The
CuH-catalyzed
hydroamination
of
alkenes
and
alkynes
using
a
silane
an
amine
transfer
reagent
represents
simple
strategy
to
access
chiral
products.
We
have
recently
reported
methods
prepare
amines
with
high
efficiency
stereoselectivity
this
approach.
However,
the
current
technology
is
limited
synthesis
trialkylamines
from
dialkylamine
reagents
(R2NOBz).
When
monoalkylamine
[RN(H)OBz]
were
used
for
secondary
amines,
competitive,
nonproductive
consumption
these
by
CuH
species
resulted
in
poor
yields.
In
paper,
we
report
design
modified
type
that
addresses
limitation.
This
effort
has
enabled
us
develop
variety
coupling
partners,
including
those
derived
amino
acid
esters,
carbohydrates,
steroids.
Mechanistic
investigations
indicated
are
less
susceptible
direct
reaction
CuH.
Journal of the American Chemical Society,
Год журнала:
2016,
Номер
138(18), С. 5793 - 5796
Опубликована: Апрель 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.
Journal of the American Chemical Society,
Год журнала:
2014,
Номер
136(8), С. 3006 - 3009
Опубликована: Фев. 6, 2014
The
direct
Ir-catalyzed
cross-coupling
between
branched,
racemic
allylic
alcohols
and
simple
olefins
is
described.
This
transformation
catalyzed
by
an
Ir–(P,olefin)
complex
proceeds
with
high
site
selectivity
excellent
enantioselectivity.
method
allows
rapid
access
to
various
1,5-dienes
or
trienes
was
used
in
the
catalytic
asymmetric
synthesis
of
γ-secretase
modulator
JNJ-40418677.
Angewandte Chemie International Edition,
Год журнала:
2016,
Номер
55(10), С. 3496 - 3499
Опубликована: Фев. 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.
Journal of the American Chemical Society,
Год журнала:
2015,
Номер
137(50), С. 15899 - 15906
Опубликована: Ноя. 25, 2015
The
first
Ir-catalyzed
intramolecular
asymmetric
allylic
dearomatization
reaction
of
pyridines,
pyrazines,
quinolines,
and
isoquinolines
has
been
developed.
Enabled
by
in
situ
formed
chiral
Ir-catalyst,
the
dearomatized
products
were
isolated
high
levels
yield
(up
to
99%
yield)
enantioselectivity
ee).
It
is
worth
noting
that
Me-THQphos
ligand
much
more
efficient
than
other
tested
ligands
for
pyrazines
certain
quinolines.
Mechanistic
studies
carried
out,
results
suggest
feasibility
an
alternative
process
which
features
formation
a
quinolinium
as
key
intermediate.
mechanistic
findings
render
this
yet
unknown
type
chemistry
Reissert-type
reactions.
In
addition,
utility
method
was
showcased
large-scale
formal
synthesis
(+)-gephyrotoxin.
Journal of the American Chemical Society,
Год журнала:
2015,
Номер
137(30), С. 9716 - 9721
Опубликована: Июль 5, 2015
The
CuH-catalyzed
hydroamination
of
alkenes
and
alkynes
using
a
silane
an
amine
transfer
reagent
represents
simple
strategy
to
access
chiral
products.
We
have
recently
reported
methods
prepare
amines
with
high
efficiency
stereoselectivity
this
approach.
However,
the
current
technology
is
limited
synthesis
trialkylamines
from
dialkylamine
reagents
(R2NOBz).
When
monoalkylamine
[RN(H)OBz]
were
used
for
secondary
amines,
competitive,
nonproductive
consumption
these
by
CuH
species
resulted
in
poor
yields.
In
paper,
we
report
design
modified
type
that
addresses
limitation.
This
effort
has
enabled
us
develop
variety
coupling
partners,
including
those
derived
amino
acid
esters,
carbohydrates,
steroids.
Mechanistic
investigations
indicated
are
less
susceptible
direct
reaction
CuH.
