Angewandte Chemie,
Journal Year:
2019,
Volume and Issue:
131(39), P. 13992 - 13997
Published: July 8, 2019
Abstract
Metal
hydride
catalyzed
hydrocarbonation
reactions
of
alkenes
are
an
efficient
approach
to
construct
new
carbon–carbon
bonds
from
readily
available
alkenes.
However,
the
regioselectivity
remains
challenging
be
controlled.
In
nickel
(NiH)
hydrocarbonation,
linear
selectivity
is
most
often
obtained
because
relative
stability
Ni–alkyl
intermediate
over
its
branched
counterpart.
Herein,
we
show
that
boronic
pinacol
ester
(Bpin)
group
directs
a
Ni‐catalyzed
occur
at
adjacent
carbon
center,
resulting
in
formal
branch
selectivity.
Both
alkyl
and
aryl
halides
can
used
as
electrophiles
this
providing
access
wide
range
secondary
Bpin
derivatives,
which
valuable
building
blocks
synthetic
chemistry.
The
utility
method
demonstrated
by
late‐stage
functionalization
natural
products
drug
molecules,
synthesis
anticancer
agent,
iterative
syntheses.
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.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(5), P. 1322 - 1345
Published: Jan. 1, 2023
Functionalization
of
alkenes/alkynes
is
a
highly
effective
route
to
achieve
molecular
complexity.
This
review
summarizes
recent
progresses
on
the
1,2-difunctionalization/hydrofunctionalization
unactivated
with
C−S
bond
formation.
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(39), P. 13860 - 13864
Published: July 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,
Journal Year:
2019,
Volume and Issue:
58(39), P. 13854 - 13859
Published: July 8, 2019
Abstract
Metal
hydride
catalyzed
hydrocarbonation
reactions
of
alkenes
are
an
efficient
approach
to
construct
new
carbon–carbon
bonds
from
readily
available
alkenes.
However,
the
regioselectivity
remains
challenging
be
controlled.
In
nickel
(NiH)
hydrocarbonation,
linear
selectivity
is
most
often
obtained
because
relative
stability
Ni–alkyl
intermediate
over
its
branched
counterpart.
Herein,
we
show
that
boronic
pinacol
ester
(Bpin)
group
directs
a
Ni‐catalyzed
occur
at
adjacent
carbon
center,
resulting
in
formal
branch
selectivity.
Both
alkyl
and
aryl
halides
can
used
as
electrophiles
this
providing
access
wide
range
secondary
Bpin
derivatives,
which
valuable
building
blocks
synthetic
chemistry.
The
utility
method
demonstrated
by
late‐stage
functionalization
natural
products
drug
molecules,
synthesis
anticancer
agent,
iterative
syntheses.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(12), P. 4959 - 4964
Published: Jan. 22, 2020
The
enantioselective
construction
of
axially
chiral
compounds
by
electrophilic
carbothiolation
alkynes
is
disclosed
for
the
first
time.
This
transformation
enabled
use
a
Ts-protected
bifunctional
sulfide
catalyst
and
Ms-protected
ortho-alkynylaryl
amines
(Ts=tosyl;
Ms=mesyl).
Both
arylthiolating
trifluoromethylthiolating
reagents
are
suitable
this
reaction.
obtained
products
vinyl-aryl
amino
sulfides
can
be
easily
converted
into
biaryl
sulfides,
sulfoxides,
amines,
other
valuable
difunctionalized
compounds.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(36), P. 14104 - 14109
Published: Aug. 28, 2019
1,2-Bis-boronic
esters
are
versatile
intermediates
that
enable
the
rapid
elaboration
of
simple
alkene
precursors.
Previous
reports
on
their
selective
mono-functionalization
have
targeted
most
accessible
position,
retaining
more
hindered
secondary
boronic
ester.
In
contrast,
we
found
photoredox-catalyzed
mono-deboronation
generates
primary
β-boryl
radicals
undergo
1,2-boron
shift
to
form
thermodynamically
favored
radicals,
allowing
for
transformation
The
pivotal
shift,
which
has
been
demonstrated
be
stereoretentive,
enables
access
a
wide
range
functionalized
and
applied
highly
diastereoselective
fragmentation
transannular
cyclization
reactions.
Furthermore,
its
generality
shown
in
radical
cascade
reaction
with
an
allylboronic
Science,
Journal Year:
2021,
Volume and Issue:
374(6568), P. 752 - 757
Published: Nov. 4, 2021
A
strategy
that
facilitates
the
construction
of
a
wide
variety
trisubstituted
stereocenters
through
catalytically
accessed
common
chiral
intermediate
could
prove
highly
enabling
for
field
synthetic
chemistry.
We
report
discovery
enantioselective,
catalytic
1,2-boronate
rearrangements
synthesis
α-chloro
pinacol
boronic
esters
from
readily
available
and
dichloromethane.
The
building
blocks
produced
in
these
reactions
can
undergo
two
sequential
stereospecific
elaborations
to
generate
assortment
stereocenters.
enantioselective
reaction
is
catalyzed
by
lithium-isothiourea-boronate
complex,
which
proposed
promote
rearrangement
dual–lithium-induced
chloride
abstraction
orchestrated
Lewis
basic
functionality
on
catalyst
scaffold.
