ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(5), P. 3232 - 3240
Published: Feb. 10, 2020
The
asymmetric
hydrogenation
of
α-boryl
enamides
has
been
developed
using
a
bisphosphine-rhodium
catalyst.
chelate
coordination
the
amido
group
to
rhodium
and
nonbonding
interactions
between
substrate
ligand
play
important
roles
afford
chiral
α-amidoboronic
esters
with
quantitative
conversions,
high
chemoselectivity,
excellent
enantioselectivity
(92–99%
ee).
Computation
catalytic
cycle
revealed
selectivity
both
in
hydrogen
activation
migratory
insertion
steps,
equally
contributing
enantioselectivity.
In
cases,
provided
by
Bpin
contributed
significantly
stabilization
transition
states
lower
energy
pathway.
Chemical Society Reviews,
Journal Year:
2019,
Volume and Issue:
48(13), P. 3464 - 3474
Published: Jan. 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,
Journal Year:
2018,
Volume and Issue:
14(3), P. 329 - 343
Published: Dec. 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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(30), P. 16508 - 16516
Published: July 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,
Journal Year:
2020,
Volume and Issue:
59(11), P. 4370 - 4374
Published: Jan. 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,
Journal Year:
2020,
Volume and Issue:
59(39), P. 16859 - 16872
Published: June 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,
Journal Year:
2019,
Volume and Issue:
58(40), P. 14245 - 14249
Published: Aug. 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.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(28), P. 9448 - 9452
Published: May 6, 2019
A
series
of
in
situ
formed
alkenyl
diboronate
complexes
from
Grignard
reagents
(commercially
available
or
prepared
bromides
and
Mg)
with
B2
Pin2
(bis(pinacolato)diboron)
react
diverse
alkyl
halides
by
a
Ru
photocatalyst
to
give
various
gem-bis(boryl)alkanes.
Alkyl
radicals
add
efficiently
the
complexes,
adduct
radical
anions
undergo
radical-polar
crossover,
specifically,
1,2-boryl-anion
shift
boron
α-carbon
sp2
center.
This
transformation
shows
good
functional-group
compatibility
can
serve
as
powerful
synthetic
tool
for
late-stage
functionalization
complex
compounds.
Measurements
quantum
yield
reveal
that
radical-chain
mechanism
is
operative
which
diboronates
acts
reductive
quencher
excited
state
photocatalyst.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(39), P. 16766 - 16775
Published: Sept. 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,
Journal Year:
2018,
Volume and Issue:
140(46), P. 15621 - 15625
Published: Nov. 9, 2018
A
catalytic,
enantioselective
method
for
the
preparation
of
chiral,
non-racemic,
alkylboronic
esters
bearing
two
vicinal
stereogenic
centers
is
described.
The
reaction
proceeds
via
a
1,2-migration
zwitterionic
thiiranium–boronate
complex
to
give
exclusively
anti
carbosulfenylation
products.
broad
scope
aryl
groups
migrate
with
good
yield
and
excellent
enantioselectivity
(up
99:1
e.r.).
Similarly,
range
di-
trisubstituted
alkenylboronic
are
competent
partners.
This
provides
access
both
secondary
tertiary
chiral
esters.
Advanced Synthesis & Catalysis,
Journal Year:
2019,
Volume and Issue:
362(11), P. 2077 - 2087
Published: Dec. 24, 2019
Abstract
1,2‐Boron
ate
rearrangements
represent
a
fundamental
class
of
transformations
to
establish
new
C−C
bonds
while
retaining
the
valuable
boron
moiety
in
product.
In
established
ionic
processes,
complex
is
activated
by
an
external
electrophile
induce
1,2‐migration
from
adjacent
sp
3
or
2
carbon
atom.
Recently,
two
complementary
radical
polar
crossover
approaches
have
been
explored
for
both
classes,
1,2‐migrations
and
centers.
This
review
describes
general
concepts
this
emerging
research
field
summarizes
recent
developments
radical‐induced
carbon.
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