Synlett,
Год журнала:
2022,
Номер
33(18), С. 1863 - 1867
Опубликована: Июль 5, 2022
Abstract
We
report
a
highly
branch-selective
and
enantioselective
allylic
alkylation
of
simple
ketones
with
racemic
aliphatic
carbonates
under
mild
conditions.
By
using
Rh–bisoxazolinephosphine
system
catalytic
amounts
base
in
THF,
series
chiral
β-branched
γ,δ-unsaturated
were
obtained
excellent
regio-
enantioselectivities.
An
outer-sphere
nucleophilic
substitution
C–C
bond-formation
process
is
proposed
on
the
basis
mechanistic
studies.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(5), С. 2039 - 2043
Опубликована: Ноя. 6, 2019
Abstract
The
stereodivergent
iridium‐catalyzed
allylic
alkylation
and
fluorination
of
acyclic
ketones
is
described.
α‐Pyridyl‐α‐fluoroketones
with
vicinal
tertiary
quaternary
stereocenters
were
obtained
in
moderate
to
excellent
yields
stereoselectivities.
Distinct
from
known
synthesis,
for
which
two
different
chiral
catalysts
are
required
general,
herein
we
report
a
sequence‐dependent
synthesis.
With
only
single
Ir
catalyst,
all
four
possible
stereoisomers
the
products
prepared
same
starting
materials
by
simply
adjusting
sequence
asymmetric
varying
absolute
configuration
catalyst.
Catalysis Science & Technology,
Год журнала:
2022,
Номер
12(13), С. 4100 - 4112
Опубликована: Янв. 1, 2022
This
minireview
describes
the
recent
progress
of
iridium-catalyzed
enantioselective
allylic
substitution
using
phosphoramidite-alkene
ligands
realizing
highly
carbon–carbon
and
carbon–heteroatom
bond
formation.
Angewandte Chemie,
Год журнала:
2019,
Номер
132(5), С. 2055 - 2059
Опубликована: Ноя. 6, 2019
Abstract
The
stereodivergent
iridium‐catalyzed
allylic
alkylation
and
fluorination
of
acyclic
ketones
is
described.
α‐Pyridyl‐α‐fluoroketones
with
vicinal
tertiary
quaternary
stereocenters
were
obtained
in
moderate
to
excellent
yields
stereoselectivities.
Distinct
from
known
synthesis,
for
which
two
different
chiral
catalysts
are
required
general,
herein
we
report
a
sequence‐dependent
synthesis.
With
only
single
Ir
catalyst,
all
four
possible
stereoisomers
the
products
prepared
same
starting
materials
by
simply
adjusting
sequence
asymmetric
varying
absolute
configuration
catalyst.
We
report
an
asymmetric
allylation
of
silyl
enol
ethers
derived
from
α-ketoesters
with
allylic
alcohols
by
iridium/chiral
(P,olefin)-ligand
catalyst.
Allylation
a
broad
range
and
formed
the
allylated
products
excellent
enantioselectivities.
Silyl
α-diketones
as
well
were
also
compatible
to
achieve
nearly
perfect
The
utility
bearing
α-ketoester
group
α-diketone
is
demonstrated
transformation
valuable
functional
groups,
exemplified
α-aminoester,
aldehyde,
2(1H)-quinoxalinone,
quinoxaline.
ChemistryOpen,
Год журнала:
2020,
Номер
9(9), С. 929 - 952
Опубликована: Сен. 1, 2020
Abstract
The
palladium‐catalyzed
allylic
alkylation
of
non‐stabilized
ketone
enolates
was
thought
for
a
long
time
to
be
not
as
efficient
the
analogous
reactions
stabilized
enolates,
e.
g.
malonates
and
β‐ketoesters.
field
has
experienced
rapid
development
during
last
two
decades,
with
range
new,
highly
protocols
evolved.
In
this
review,
early
developments
well
current
methods
applications
enolate
allylations
will
discussed.
Organic Letters,
Год журнала:
2024,
Номер
26(2), С. 508 - 513
Опубликована: Янв. 5, 2024
The
enantioselective
allylic
alkylation
of
nitro
ketene
aminals
with
racemic
alcohols
was
realized
by
iridium/acid
dual
catalysis.
An
allyl
group
installed
on
the
α-position
in
a
branched-selective
manner
high
efficiency
excellent
enantioselectivities
(93–99%
ee).
protocol
applied
to
late-stage
modification
neonicotinoid
insecticides,
which
directly
furnished
novel
analogue
good
insecticidal
activity
against
Aphis
craccivora
(LC50
=
6.40
mg/L).
On
basis
control
experiment,
an
aza-ene-type
reaction
mechanism
proposed.
Chemical Science,
Год журнала:
2021,
Номер
12(8), С. 3070 - 3075
Опубликована: Янв. 1, 2021
The
first
iridium-catalyzed
enantioselective
allylic
alkylation
of
an
olefinic
C(sp2)–H
bond
–
that
α,β-unsaturated
carbonyl
compound,
is
developed
in
cooperation
with
Lewis
base
catalysis.
Chemical Science,
Год журнала:
2022,
Номер
13(42), С. 12491 - 12497
Опубликована: Янв. 1, 2022
Hydroxy-directed
iridium-catalyzed
enantioselective
formal
β-C(sp2)-H
allylic
alkylation
of
kojic
acid
and
structurally
related
α,β-unsaturated
carbonyl
compounds
is
developed.
This
reaction,
catalyzed
by
an
Ir(i)/(P,olefin)
complex,
utilizes
the
nucleophilic
character
α-hydroxy
carbonyls,
to
introduce
allyl
group
at
its
β-position
in
a
branched-selective
manner
good
excellent
yield
with
uniformly
high
enantioselectivity
(up
>99.9
:
0.1
er).
To
best
our
knowledge,
this
report
represents
first
example
use
transition
metal
highly
transformation.
Catalysis Reviews,
Год журнала:
2020,
Номер
64(4), С. 679 - 715
Опубликована: Окт. 25, 2020
In
the
past
three
decades,
rare-earth
metal
triflates
including
scandium
triflate,
yttrium
and
lanthanide
(La−Lu)
were
widely
employed
in
organic
chemistry,
such
as
cyclization,
C-H
bond
functionalization
types
of
reactions.
Recently,
approaches
using
catalysts
have
been
mainly
focusing
on
(1)
achieving
high
regioselectivity
stereoselectivity
with
effective
ligands
(2)
further
extending
reaction
scope
by
cooperation
other
transition
catalysts.
This
review
focuses
recent
advances
triflates-catalyzed
reactions
from
2017
to
2019.
also
emphasis
transformations
related
mechanisms
show
general
readership
about
capabilities,
challenges
well
potential
applications.
Chemical Communications,
Год журнала:
2021,
Номер
57(84), С. 11080 - 11083
Опубликована: Янв. 1, 2021
We
report
herein
an
iridium-catalyzed
asymmetric
allylic
esterification
of
racemic
secondary
alcohols
using
free
carboxylic
acids
as
nucleophiles
under
mild
conditions
with
broad
functional
group
tolerance,
exhibiting
excellent
regio-
and
enantioselectivity
.
