Abstract
Asymmetric
multicomponent
reactions
are
considered
as
efficient
protocols
for
constructing
complex
chiral
molecules
because
of
their
step‐
and
atom‐economy.
Nickel‐catalyzed
asymmetric
three‐component
dicarbofunctionalization
alkenes
has
been
well
developed
in
recent
years,
which
is
used
the
area
total
synthesis
natural
products
late‐stage
modification
drugs
rapid
incorporation
sp
3
‐enriched
carbon
centers.
In
this
concept,
significant
breakthroughs
field
summarized,
together
with
related
mechanisms.
Moreover,
remaining
challenges
potential
opportunities
also
highlighted.
Chemical Society Reviews,
Год журнала:
2019,
Номер
48(13), С. 3464 - 3474
Опубликована: Янв. 1, 2019
This
tutorial
review
describes
recent
developments
in
catalytic
reaction
design
that
involve
catalyst-promoted
1,2-metalate
shifts
as
a
critical
part
of
the
mechanism.
Chemistry - An Asian Journal,
Год журнала:
2018,
Номер
14(3), С. 329 - 343
Опубликована: Дек. 12, 2018
Abstract
Organoboron
compounds
have
become
one
of
the
most
versatile
building
blocks
in
organic
synthesis
owing
to
their
accessible
and
efficient
conversion
into
many
different
functional
groups.
In
particular,
alkenyl
boronates
received
a
great
deal
attention
as
very
reactive
substrates
Suzuki–Miyaura
cross‐coupling
reactions.
Accordingly,
efforts
towards
development
methods
prepare
this
type
compound
are
ongoing.
contribution,
progress
search
for
synthetic
routes
use
variety
transformations
is
accounted.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(23), С. 13129 - 13188
Опубликована: Янв. 1, 2021
We
provide
a
comprehensive
overview
of
transition
metal-catalysed
asymmetric
borylation
processes
to
construct
C–B,
C–C,
and
other
C–heteroatom
bonds
with
considerable
attention
devoted
the
reaction
modes
mechanisms
involved.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16508 - 16516
Опубликована: Июль 20, 2023
Enantioenriched
organoboron
intermediates
are
important
building
blocks
in
organic
synthesis
and
drug
discovery.
Recently,
transition
metal-catalyzed
enantioselective
1,2-metalate
rearrangements
of
alkenylboronates
have
emerged
as
an
attractive
protocol
to
access
these
valuable
reagents
by
installing
two
different
carbon
fragments
across
C═C
π-bonds.
Herein,
we
report
the
development
iridium-catalyzed
asymmetric
allylation-induced
rearrangement
bicyclo[1.1.0]butyl
(BCB)
boronate
complexes
enabled
strain
release,
which
allows
difunctionalization
C-C
σ-bonds,
including
dicarbonation
carboboration.
This
provides
a
variety
enantioenriched
three-dimensional
1,1,3-trisubstituted
cyclobutane
products
bearing
boronic
ester
that
can
be
readily
derivatized.
Notably,
reaction
gives
trans
diastereoisomers
result
from
anti-addition
σ-bond,
is
contrast
syn-additions
observed
for
reactions
promoted
PdII-aryl
other
electrophiles
our
previous
works.
The
diastereoselectivity
has
been
rationalized
based
on
combination
experimental
data
density
functional
theory
calculations,
suggest
BCB
highly
nucleophilic
react
via
early
states
with
low
activation
barriers.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(11), С. 4370 - 4374
Опубликована: Янв. 7, 2020
A
modular,
site-selective
1,2-dicarbofunctionalization
of
vinyl
boronates
with
organic
halides
through
dual
catalysis
is
described.
This
reaction
proceeds
under
mild
conditions
and
characterized
by
excellent
chemo-
regioselectivity.
It
thus
represents
a
complementary
new
technique
for
preparing
densely
functionalized
alkyl
boron
architectures
from
simple
accessible
precursors.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(39), С. 16859 - 16872
Опубликована: Июнь 27, 2020
The
stereospecific
1,2-migration
of
boronate
complexes
is
one
the
most
representative
reactions
in
boron
chemistry.
This
process
has
been
used
extensively
to
develop
powerful
methods
for
asymmetric
synthesis,
with
applications
spanning
from
pharmaceuticals
natural
products.
Typically,
driven
by
displacement
an
α-leaving
group,
oxidation
α-boryl
radical,
or
electrophilic
activation
alkenyl
complex.
aim
this
article
summarize
recent
advances
rapidly
expanding
field
electrophile-induced
groups
sp
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(39), С. 13860 - 13864
Опубликована: Июль 9, 2019
The
direct
and
selective
functionalization
of
relatively
simple
readily
accessible
precursors
to
produce
highly
functionalized
alkyl
boronates
is
a
synthetically
useful
process.
Herein
we
report
NiH-catalyzed
remote
hydroarylation
process
that
can,
through
synergistic
combination
chain
walking
subsequent
cross-coupling,
introduce
an
aryl
group
at
the
adjacent
carbon
atom
under
mild
conditions.
By
means
preliminary
experiment
with
moderate
enantioselectivity,
it
was
shown
asymmetric
version
could
also
be
realized.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(40), С. 14245 - 14249
Опубликована: Авг. 7, 2019
Abstract
A
hybrid
transition‐metal/radical
process
is
described
that
results
in
the
addition
of
organozinc
reagents
and
alkyl
halides
across
alkenyl
boron
an
enantioselective
catalytic
fashion.
The
reaction
can
be
accomplished
both
intermolecularly
intramolecularly,
providing
useful
product
yields
high
enantioselectivities
manifolds.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(39), С. 16766 - 16775
Опубликована: Сен. 4, 2020
Difunctionalization
reactions
of
C–C
σ-bonds
have
the
potential
to
streamline
access
molecules
that
would
otherwise
be
difficult
prepare.
However,
development
such
is
challenging
because
are
typically
unreactive.
Exploiting
high
ring-strain
energy
polycyclic
carbocycles
a
common
strategy
weaken
and
facilitate
reaction
σ-bonds,
but
there
limited
examples
highly
strained
being
used
in
difunctionalization
reactions.
We
demonstrate
bicyclo[1.1.0]butyl
boronate
complexes
(strain
ca.
65
kcal/mol),
which
were
prepared
by
reacting
boronic
esters
with
lithium,
react
electrophiles
achieve
diastereoselective
central
σ-bond
unit.
The
shows
broad
substrate
scope,
range
different
successfully
employed
form
diverse
set
1,1,3-trisubstituted
cyclobutanes
(>50
examples)
diastereoselectivity.
diastereoselectivity
observed
has
been
rationalized
based
on
combination
experimental
data
DFT
calculations,
suggests
separate
concerted
stepwise
mechanisms
operating,
depending
upon
migrating
substituent
electrophile
used.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(46), С. 19652 - 19659
Опубликована: Ноя. 4, 2020
A
copper-catalyzed
enantioconvergent
Suzuki–Miyaura
C(sp3)–C(sp2)
cross-coupling
of
various
racemic
alkyl
halides
with
organoboronate
esters
has
been
established
in
high
enantioselectivity.
Critical
to
the
success
is
use
a
chiral
cinchona
alkaloid-derived
N,N,P-ligand
for
not
only
enhancing
reducing
capability
copper
catalyst
favor
stereoablative
radical
pathway
over
stereospecific
SN2-type
process
but
also
providing
an
ideal
environment
achieve
challenging
enantiocontrol
highly
reactive
species.
The
reaction
broad
scope
respect
both
coupling
partners,
covering
aryl-
and
heteroarylboronate
esters,
as
well
benzyl-,
heterobenzyl-,
propargyl
bromides
chlorides
good
functional
group
compatibility.
Thus,
it
provides
expedient
access
toward
range
useful
enantioenriched
skeletons
featuring
tertiary
benzylic
stereocenters.