Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(25)
Published: April 21, 2022
Abstract
A
new
strategy
for
the
synthesis
of
highly
versatile
cyclobutylboronates
via
photosensitized
[2+2]‐cycloaddition
alkenylboronates
and
alkenes
is
presented.
The
process
mechanistically
different
from
other
processes
in
that
energy
transfer
occurs
with
alkenylboronate
as
opposed
to
alkene.
This
allows
an
array
diverse
cyclobutylboronates.
conversion
these
adducts
compounds
well
their
utility
melicodenine
C
demonstrated.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(6), P. 4162 - 4184
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
summary
of
recent
advances
in
nickel-catalyzed
reactions
employing
tertiary
alkyl
electrophiles
for
the
construction
quaternary
carbon
centers.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(22), P. 3246 - 3259
Published: Nov. 1, 2023
ConspectusChain-walking
offers
extensive
opportunities
for
innovating
synthetic
methods
that
involve
constructing
chemical
bonds
at
unconventional
sites.
This
approach
provides
previously
inaccessible
retrosynthetic
disconnections
in
organic
synthesis.
Through
chain-walking,
transition
metal-catalyzed
alkene
difunctionalization
reactions
can
take
place
a
1,n-addition
(n
≠
2)
mode.
Unlike
classical
1,2-regioselective
reactions,
there
remains
scarcity
of
reports
regarding
migratory
patterns.
Moreover,
the
range
olefins
utilized
these
studies
is
quite
limited.About
five
years
ago,
our
research
group
embarked
on
project
aimed
developing
valuable
alkenes
through
chain-walking.
Our
focus
was
carboboration
utilizing
nickel
catalysis.
The
reaction
commences
with
insertion
an
olefin
into
Ni-Bpin
species.
Subsequently,
thermodynamically
stable
alkyl
complex
generated
chain-walking
process.
then
couples
carbon-based
electrophile,
leading
to
formation
alkylboron
compound.
It
worth
highlighting
success
transformations
relies
significantly
utilization
bisnitrogen-based
ligand
and
LiOMe
as
B2pin2
activator.
Synthetically,
establish
robust
platform
rapid
efficient
synthesis
wide
structurally
diverse
organoboron
compounds,
which
are
not
facially
accessed
by
conventional
methods.
incorporation
versatile
boron
introduces
wealth
possibilities
subsequent
diversifications,
enhancing
value
resulting
products
allowing
creation
broader
derivatives
applications.This
Account
comprehensive
overview
efforts
advancements
field
unactivated
using
We
begin
outlining
development
series
1,1-regioselective
terminal
alkenes.
A
significant
placed
initial
integration
boronate,
only
triggers
metal
species
but
also
exerts
control
over
remote
stereochemistry
involving
substituted
methylenecyclohexenes.
Continuing
exploration,
remarkable
achieved
1,3-regio-
cis-stereoselectivity
when
dealing
cyclic
Remarkably,
catalysis
enables
heterocyclic
be
viable
coupling
partners
within
transformations.
it
grants
us
ability
achieve
regioselectivity
cyclohexenes
unattainable,
thus
expanding
horizons
regiochemical
reactions.
Lastly,
we
present
evolution
ligand-modulated
regiodivergent
allylarenes.
By
gaining
insights
underlying
mechanisms
driving
regiodivergence,
lay
strong
foundation
tackling
challenges
related
selecting
specific
sites
especially
multiple
factors.
anticipate
findings,
coupled
mechanistic
we've
gained,
will
advance
realm
contribute
understanding
selectivity
this
nature.
advancement
catalyze
intricate
functional
molecules,
contributing
compounds
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(47), P. 17068 - 17073
Published: Sept. 20, 2019
Abstract
We
report
the
development
of
palladium(0)‐catalyzed
syn
‐selective
1,2‐carboboration
and
‐silylation
reactions
alkenes
containing
cleavable
directing
groups.
With
B
2
pin
or
PhMe
Si‐Bpin
as
nucleophiles
aryl/alkenyl
triflates
electrophiles,
a
broad
range
mono‐,
di‐,
tri‐
tetrasubstituted
are
compatible
in
these
transformations.
further
describe
directed
dearomative
electron‐rich
heteroarenes
by
employing
this
approach.
Through
use
removable
chiral
group,
we
demonstrate
viability
achieving
stereoinduction
Heck‐type
alkene
1,2‐difunctionalization.
This
work
introduces
new
avenues
to
access
highly
functionalized
boronates
silanes
with
precise
regio‐
stereocontrol.
Israel Journal of Chemistry,
Journal Year:
2019,
Volume and Issue:
60(3-4), P. 219 - 229
Published: Sept. 10, 2019
Abstract
During
the
past
decade,
many
research
groups
have
described
catalytic
methods
for
1,2‐carboboration,
allowing
access
to
structurally
complex
organoboronates
from
alkenes.
Various
transition
metals,
especially
copper,
palladium,
and
nickel,
been
widely
used
in
these
reactions.
This
review
summarizes
advances
this
field,
with
a
special
focus
on
cycles
involved
different
metal‐catalyzed
carboboration
reactions,
as
well
regio‐
stereochemical
consequences
of
underlying
mechanisms.
1,2‐Carboboration
other
unsaturated
systems,
such
alkynes
allenes,
is
outside
scope
review.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(48), P. 20027 - 20034
Published: Nov. 4, 2021
Whereas
there
is
a
significant
interest
in
the
rapid
construction
of
diversely
substituted
saturated
heterocycles,
direct
and
modular
access
currently
limited
to
mono-,
2,3-,
or
3,4-substitution
pattern.
This
Communication
describes
straightforward
2,4-substituted
heterocycles
from
readily
available
materials
highly
stereo-
regioselective
manner,
which
sets
stage
for
numerous
accessible
drug
motifs.
The
strategy
relies
on
chain
walking
catalysis.
Chemistry - A European Journal,
Journal Year:
2021,
Volume and Issue:
27(62), P. 15277 - 15326
Published: Sept. 9, 2021
Abstract
This
review
discusses
recent
advances
in
the
chemistry
of
saturated
boronic
acids,
boronates,
and
trifluoroborates.
Applications
title
compounds
design
boron‐containing
drugs
are
surveyed,
with
special
emphasis
on
α‐amino
derivatives.
A
general
overview
as
modern
tools
to
construct
C(sp
3
)−C
)‐heteroatom
bonds
is
given,
including
developments
Suzuki‐Miyaura
Chan‐Lam
cross‐couplings,
single‐electron‐transfer
processes
metallo‐
organocatalytic
photoredox
reactions,
transformations
boron
“ate”
complexes.
Finally,
an
attempt
summarize
current
state
art
synthesis
trifluoroborates
made,
a
brief
mention
“classical”
methods
(transmetallation
organolithium/magnesium
reagents
species,
anti‐Markovnikov
hydroboration
alkenes,
modification
alkenyl
compounds)
focus
methodologies
(boronation
alkyl
(pseudo)halides,
derivatives
carboxylic
alcohols,
primary
amines,
boronative
C−H
activation,
novel
approaches
alkene
hydroboration,
1,2‐metallate‐type
rearrangements).
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(21), P. 11740 - 11744
Published: Feb. 25, 2021
Abstract
A
catalytic
1,1‐difunctionalization
of
unactivated
olefins
en
route
to
sp
3
bis
‐organometallic
B,B(Si)‐reagents
is
described.
The
protocol
characterized
by
exceptional
reaction
rates,
mild
conditions,
wide
scope,
and
exquisite
selectivity
pattern,
constituting
a
new
platform
access
‐organometallics.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(3), P. 2058 - 2063
Published: Jan. 24, 2022
A
preeminent
challenge
in
alkene
difunctionalization
is
the
control
of
regio-,
diastereo-,
and
enantioselectivity.
In
this
Perspective,
a
Pd/Cu-cooperative
catalytic
system
for
arylboration
highlighted
that
allows
controlled
introduction
substituents.
particular,
examples
allowed
divergent
reactivity
from
single
substrate
based
on
tuning
catalysts
reaction
conditions
are
emphasized.
