Synergistic Hydrocobaltation and Borylcobaltation Enable Regioselective Migratory Triborylation of Unactivated Alkenes
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(14)
Опубликована: Янв. 28, 2022
The
structural
diversity
of
sp3
-triorganometallic
reagents
enhances
their
potentiality
in
the
modular
construction
molecular
complexity
chemical
synthesis.
Despite
significant
achievements
on
preparation
1,1,1-
and
1,1,2-triorganometallic
B,B,B-reagents,
catalytic
approaches
that
enable
installation
multiple
boryl
groups
at
skipped
carbons
unactivated
alkenes
still
remain
elusive.
Herein,
we
report
a
cobalt-catalyzed
selective
triborylation
reaction
to
access
synthetically
versatile
1,1,3-triborylalkanes.
This
protocol
provides
general
platform
for
regioselective
trifunctionalization
alkenes,
its
utility
is
highlighted
by
synthesis
various
value-added
chemicals
from
readily
accessible
alkenes.
Mechanistic
studies,
including
deuterium-labelling
experiments
evaluation
potential
reactive
intermediates,
provide
insight
into
experimentally
observed
chemo-
regioselectivity.
Язык: Английский
Cobalt‐Catalyzed One‐Pot Asymmetric Difunctionalization of Alkynes to Access Chiral gem‐(Borylsilyl)alkanes
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(38), С. 20684 - 20688
Опубликована: Июль 5, 2021
Abstract
Enantioselective
cobalt‐catalyzed
one‐pot
hydrosilylation
and
hydroboration
of
terminal
alkynes
has
been
developed
employing
a
cobalt
catalyst
generated
from
Co(acac)
2
(
R
,
)‐Me‐Ferrocelane.
A
variety
undergo
this
asymmetric
transformation,
affording
the
corresponding
gem
‐(borylsilyl)alkane
products
with
high
enantioselectivity
(up
to
98
%
ee
).
This
reaction
combines
E
)‐selective
consecutive
enantioselective
)‐vinylsilanes
one
chiral
catalyst.
protocol
represents
most
straightforward
approach
access
versatile
‐(borylsilyl)alkanes
readily
available
commercially
salt
ligand.
Язык: Английский
Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β‐Acetoxy Elimination
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(46), С. 24500 - 24504
Опубликована: Сен. 12, 2021
Palladium-catalyzed
remote
arylative
substitution
was
achieved
for
the
reaction
of
arylboronic
acids
with
alkenes
possessing
a
distant
acetoxy
group
to
provide
arylation
products
having
an
alkene
moiety
at
position.
The
use
β-acetoxy
elimination
as
key
step
in
catalytic
cycle
allowed
regioselective
formation
unstabilized
after
chain
walking.
This
applicable
various
well
substrates.
Язык: Английский
Synergistic Hydrocobaltation and Borylcobaltation Enable Regioselective Migratory Triborylation of Unactivated Alkenes
Angewandte Chemie,
Год журнала:
2022,
Номер
134(14)
Опубликована: Янв. 28, 2022
Abstract
The
structural
diversity
of
sp
3
‐triorganometallic
reagents
enhances
their
potentiality
in
the
modular
construction
molecular
complexity
chemical
synthesis.
Despite
significant
achievements
on
preparation
1,1,1‐
and
1,1,2‐triorganometallic
B,B,B‐reagents,
catalytic
approaches
that
enable
installation
multiple
boryl
groups
at
skipped
carbons
unactivated
alkenes
still
remain
elusive.
Herein,
we
report
a
cobalt‐catalyzed
selective
triborylation
reaction
to
access
synthetically
versatile
1,1,3‐triborylalkanes.
This
protocol
provides
general
platform
for
regioselective
trifunctionalization
alkenes,
its
utility
is
highlighted
by
synthesis
various
value‐added
chemicals
from
readily
accessible
alkenes.
Mechanistic
studies,
including
deuterium‐labelling
experiments
evaluation
potential
reactive
intermediates,
provide
insight
into
experimentally
observed
chemo‐
regioselectivity.
Язык: Английский
Cobalt‐Catalyzed One‐Pot Asymmetric Difunctionalization of Alkynes to Access Chiral gem‐(Borylsilyl)alkanes
Angewandte Chemie,
Год журнала:
2021,
Номер
133(38), С. 20852 - 20856
Опубликована: Июль 5, 2021
Abstract
Enantioselective
cobalt‐catalyzed
one‐pot
hydrosilylation
and
hydroboration
of
terminal
alkynes
has
been
developed
employing
a
cobalt
catalyst
generated
from
Co(acac)
2
(
R
,
)‐Me‐Ferrocelane.
A
variety
undergo
this
asymmetric
transformation,
affording
the
corresponding
gem
‐(borylsilyl)alkane
products
with
high
enantioselectivity
(up
to
98
%
ee
).
This
reaction
combines
E
)‐selective
consecutive
enantioselective
)‐vinylsilanes
one
chiral
catalyst.
protocol
represents
most
straightforward
approach
access
versatile
‐(borylsilyl)alkanes
readily
available
commercially
salt
ligand.
Язык: Английский
Zirconium Catalyzed Transformations Using Organoboron
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(25)
Опубликована: Май 30, 2022
Abstract
Organoboron
compounds
have
extreme
potential
for
organic
synthesis.
Ready
functionalization
of
organoboron
intrigued
people
to
develop
various
protocols
their
Over
the
last
several
decades,
there
has
been
a
substantial
development
in
synthesizing
new
using
transition
metals.
Among
metals,
zirconium
also
found
catalyze
diverse
reactions
organoboron.
The
chemistry
become
more
popular
with
metallocenes,
particularly
bis(cyclopentadienyl)zirconocene
chloride
hydride,
well‐known
Schwartz
reagent.
These
metallocenes
possess
significant
role
hydrozirconation,
hydroboration,
hydrogenation,
carbozirconation,
and
promising
tri‐
n
‐butyl
tin
hydride
alternative.
This
minireview
focuses
on
transformations
employing
catalysts
that
developed
so
far.
Язык: Английский
Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β‐Acetoxy Elimination
Angewandte Chemie,
Год журнала:
2021,
Номер
133(46), С. 24705 - 24709
Опубликована: Сен. 12, 2021
Abstract
Palladium‐catalyzed
remote
arylative
substitution
was
achieved
for
the
reaction
of
arylboronic
acids
with
alkenes
possessing
a
distant
acetoxy
group
to
provide
arylation
products
having
an
alkene
moiety
at
position.
The
use
β‐acetoxy
elimination
as
key
step
in
catalytic
cycle
allowed
regioselective
formation
unstabilized
after
chain
walking.
This
applicable
various
well
substrates.
Язык: Английский
Synthesis of 3-Borylated Cyclobutanols from Epihalohydrins or Epoxy Alcohol Derivatives
Опубликована: Июнь 9, 2022
There
is
an
increasing
interest
in
cyclobutanes
within
the
medicinal
chemistry
community.
Therefore,
methods
to
prepare
that
contain
synthetic
handles
for
further
elaboration
are
of
interest.
Herein,
we
report
a
new
approach
synthesis
3-borylated
cyclobutanols
via
formal
[3+1]-cycloaddition
using
readily
accessible
1,1-diborylalkanes
and
epihalohydrins
or
epoxy
alcohol
derivatives.
1-Substituted
epibromohydrin
starting
materials
provide
access
borylated
containing
substituents
at
three
four
positions
on
cyclobutane
core,
enantioenriched
epibromohydrins
lead
with
high
levels
enantiospecificity
(>98%
es).
Finally,
derivatization
studies
demonstrate
utility
both
OH
Bpin
handles.
Язык: Английский