Catalytic Enantioselective Friedel-Crafts Allenylic Alkylation
Опубликована: Ноя. 9, 2023
The
first
catalytic
enantioselective
Friedel-Crafts
(FC)
allenylic
alkylation
for
the
creation
of
central
chirality
has
been
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
Using
racemic
alcohol
as
electrophile,
this
enantioconvergent
reaction
proceeds
through
an
Ir(I)-stabilized
carbocation
intermediate,
which
is
intercepted
with
a
variety
electron-rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5:0.5
er)
1,1-disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
This
protocol
allows
formal
introduction
4
alkane
chains
into
stereocenter.
An
intramolecular
version
FC
also
shown
proceed
promising
enantioselectivity
same
conditions.
Язык: Английский
Rational design of naphthoquinone-based antibacterial agents through iridium-catalyzed enantioselective β-allenylation of 2-hydroxynaphthoquinones
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5107 - 5115
Опубликована: Янв. 1, 2024
The
first
Ir-catalyzed
enantioselective
β-allenylation
of
2-hydroxynaphthoquinones
is
developed.
β-allenylic
lawsone
derivatives
displayed
remarkable
potency
against
Gram-positive
MRSA
strain
and
low
toxicity
mammalian
cell
lines.
Язык: Английский
Catalytic Enantioselective Friedel‐Crafts Allenylation
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(47)
Опубликована: Авг. 7, 2024
Abstract
The
first
enantioselective
Friedel‐Crafts
(FC)
allenylation
reaction
for
the
creation
of
central
chirality
is
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
This
enantioconvergent
utilizes
racemic
allenylic
alcohol
as
electrophile
shows
compatibility
with
a
variety
electron‐rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5
:
0.5
e.r.)
1,1‐disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
protocol
allows
formal
introduction
4‐carbon
alkyl
chain
into
(hetero)arenes,
along
stereocenter.
Judicious
synthetic
elaborations
not
only
lead
FC
alkylation
products
less
but
also
substituted
in
ortho
‐
even
meta
‐selective
fashion.
An
intramolecular
version
this
shown
proceed
promising
enantioselectivity
same
catalytic
conditions.
Mechanistic
studies
revealed
involvement
dynamic
kinetic
asymmetric
transformation
(DyKAT)
alcohols
reaction.
Язык: Английский
Catalytic Enantioselective Friedel‐Crafts Allenylation
Angewandte Chemie,
Год журнала:
2024,
Номер
136(47)
Опубликована: Авг. 7, 2024
Abstract
The
first
enantioselective
Friedel‐Crafts
(FC)
allenylation
reaction
for
the
creation
of
central
chirality
is
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
This
enantioconvergent
utilizes
racemic
allenylic
alcohol
as
electrophile
shows
compatibility
with
a
variety
electron‐rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5
:
0.5
e.r.)
1,1‐disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
protocol
allows
formal
introduction
4‐carbon
alkyl
chain
into
(hetero)arenes,
along
stereocenter.
Judicious
synthetic
elaborations
not
only
lead
FC
alkylation
products
less
but
also
substituted
in
ortho
‐
even
meta
‐selective
fashion.
An
intramolecular
version
this
shown
proceed
promising
enantioselectivity
same
catalytic
conditions.
Mechanistic
studies
revealed
involvement
dynamic
kinetic
asymmetric
transformation
(DyKAT)
alcohols
reaction.
Язык: Английский