Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
An
expedient
synthesis
of
α-aminoboronic
acid
derivatives
via
cobalt-catalyzed
remote
site-selective
hydroboration
unactivated
alkenes
is
described
herein.
The
strategy
characterized
by
its
simplicity,
site-selectivity,
and
wide
substrate
scope,
as
both
terminal
internal
could
undergo
the
reaction
smoothly,
affording
corresponding
products
in
good
yields.
According
to
mechanism,
Co-H
generated
from
Co(acac)2
presence
HBpin,
which
starts
chain-walking
a
series
alkene
insertion
β-H
elimination
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(35)
Published: July 10, 2023
While
chain-walking
stimulates
wide
interest
in
both
polymerization
and
organic
synthesis,
site-
stereoselective
control
of
on
rings
is
still
a
challenging
task
the
realm
organometallic
catalysis.
Inspired
by
controllable
cyclohexane
olefin
polymerization,
we
have
developed
set
carboborations
cyclohexenes
based
nickel
Different
from
1,4-trans-selectivity
disclosed
polymer
science,
high
level
1,3-regio-
cis-stereoselectivity
obtained
our
reactions.
Mechanistically,
discovery
that
base
affects
reduction
ability
B2
pin2
different
bases
lead
to
catalytic
cycles
regioselective
products
(1,2-
Vs
1,3-addition).
This
study
provides
concise
modular
method
for
synthesis
1,3-disubstituted
cyclohexylboron
compounds.
The
incorporation
readily
modifiable
boronate
group
greatly
enhances
value
this
method,
synthetic
potential
which
was
highlighted
series
high-valued
commercial
chemicals
pharmaceutically
interesting
molecules.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(25), P. 17140 - 17149
Published: June 12, 2024
Enantioselective
three-component
difunctionalization
of
alkenes
with
boron
reagents
represents
an
attractive
strategy
for
assembling
three-dimensional
chiral
organoboron
compounds.
However,
regio-
and
enantiocontrol
comprise
the
pivot
challenges
in
these
transformations,
which
predominantly
require
use
activated
conjugated
alkenes.
Herein,
by
utilizing
various
carbonyl
directing
groups,
including
amides,
sulfinamides,
ketones,
esters,
we
succeed
realizing
a
nickel-catalyzed
1,2-borylalkynylation
unactivated
to
enable
simultaneous
incorporation
entity
sp-fragment
across
double
bond.
The
products
contain
boryl,
alkynyl,
functional
groups
orthogonal
synthetic
reactivities,
offering
three
handles
further
derivatization
access
valuable
intermediates.
utility
this
ligand-enabled
asymmetric
protocol
has
been
highlighted
through
late-stage
decoration
drug-relevant
molecules.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: June 30, 2023
Chain
walking
has
been
an
efficient
route
to
realize
the
functionalization
of
inert
C(sp3
)-H
bonds,
but
this
strategy
is
limited
mono-olefin
migration
and
functionalization.
Herein,
we
demonstrate
feasibility
tandem
directed
simultaneous
migrations
remote
olefins
stereoselective
allylation
for
first
time.
The
adoption
palladium
hydride
catalysis
secondary
amine
morpholine
as
solvent
critical
achieving
high
substrate
compatibility
stereochemical
control
with
method.
protocol
also
applicable
three
vicinal
bonds
thus
construct
continuous
stereocenters
along
a
propylidene
moiety
via
short
synthetic
process.
Preliminary
mechanistic
experiments
corroborated
design
dienes.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(34), P. 18722 - 18730
Published: Aug. 15, 2023
Selective
transformation
of
alkyne
triple
bonds
to
double
serves
as
an
efficient
platform
construct
substituted
alkenes.
While
significant
advances
have
been
made
in
its
spatiotemporal
regulation,
achieving
a
multicomponent
enantioselective
reaction
that
requires
multifaceted
selectivity
issues
be
overcome
is
still
uncommon.
Here,
we
report
unprecedented
asymmetric
anti-stereoselective
borylcarbofunctionalization
terminal
alkynes
by
nickel
catalysis.
The
utilization
inexpensive
chiral
diamine
ligand
enables
the
three-component
cross-coupling
alkynes,
diboron
reagent,
and
prochiral
alkyl
electrophiles
with
high
levels
regio-,
stereo-,
enantioselectivities.
This
provides
protocol
access
enantioenriched
alkenyl
esters
bearing
α-stereogenic
center,
remarkably
practical,
has
broad
scope
outstanding
functional
group
compatibility.
In
addition,
value
this
method
highlighted
diversity
follow-up
stereoretentive
derivatizations
stereoselective
concise
synthesis
complex
drug
molecules.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
366(4), P. 593 - 602
Published: Dec. 7, 2023
Abstract
Unactivated
olefins
rank
amongst
the
most
important
feedstocks
in
organic
synthesis.
Their
availability
makes
them
particularly
useful
synthons
for
subsequent
functionalization,
a
catalytic
manner.
Driven
by
popularity
ascribed
nickel
catalysis
as
new
tool
to
rapidly
forge
molecular
architectures
via
one‐or
two‐electron
manifolds,
recent
years
have
witnessed
significant
advances
Ni‐catalyzed
olefin
difunctionalization.
While
1,2‐difunctionalization
or
remote
functionalization
“chain‐walk”
become
mature
disciplines
repurposing
potential
of
building
blocks,
it
was
only
recently
that
extensions
this
chemistry
1,1‐difunctionalization
been
possible.
This
review
summarizes
1,1‐difunctionalization,
holding
considerable
promise
powerful
strategy
our
ever‐growing
synthetic
repertoire.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 12132 - 12137
Published: Sept. 21, 2022
A
catalytic
monofluoroalkylation
of
terminal
and
internal
olefins
is
described.
This
protocol
distinguished
by
its
mild
conditions,
wide
scope─including
the
utilization
chemical
feedstocks
advanced
intermediates─and
exquisite
site-selectivity
for
both
α-olefins
olefins.
In
latter,
C–C
bond
formation
occurs
at
remote
sp3
C–H
sites,
thus
unlocking
a
blueprint
incorporating
monofluorinated
alkyl
chains
that
complements
existing
techniques
occurring
centers.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(7), P. 4569 - 4580
Published: March 21, 2023
Organoboron
showed
great
potential
in
the
synthesis
of
various
high-value
chemical
compounds.
Direct
hydroboration
olefins
has
been
witnessed
over
time
as
a
mainstream
method
for
organoboron
In
this
work,
an
electroreductive
anti-Markovnikov
approach
with
readily
available
B2pin2
to
synthesize
valuable
compounds
high
chemo-
and
regioselectivities
under
metal
catalyst-free
conditions
was
reported.
This
protocol
exhibited
broad
substrate
scope
good
functional-group
tolerance
on
styrenes
heteroaromatic
olefins,
providing
synthetically
useful
alkylborons
efficiency
even
deuterium
borylation
products
D-incorporation
when
CD3CN
employed
solvent.
Furthermore,
gram-scale
reactions
extensive
functional
derivatization
further
highlighted
method.
Chem,
Journal Year:
2023,
Volume and Issue:
9(8), P. 2222 - 2236
Published: May 4, 2023
Asymmetric
cross-coupling
involving
sp3-hybridized
carbon
nucleophiles
has
become
one
of
the
most
powerful
methods
for
synthesis
chiral
C(sp3)-enriched
three-dimensional
(3D)
structures,
which
are
essential
scaffolds
pharmaceuticals,
agrochemicals,
and
functional
materials.
To
date,
in
contrast
to
application
several
alkyl
organometallic
(e.g.,
alkyl-zinc,
boron,
magnesium)
asymmetric
cross-couplings,
more
easily
accessible
alkylzirconocene
reagents
have
received
much
less
attention.
Herein,
we
report
a
visible-light-induced,
Ni-catalyzed,
gem-borazirconocene
alkenes
with
aryl
unactivated
halides,
furnishing
diverse
series
valuable
alkylboron
compounds
good
yield
excellent
enantioselectivity.
Additionally,
mechanistic
investigations,
including
DFT
calculations,
radical
trapping,
kinetic
experiments,
show
how
inherent
photoreactivity
alkyl-Zr
controls
generation
step
that
is
cross-coupling,
unveiling
an
efficient
means
highly
stereoconvergent,
alkene-based,
single-electron
transformations.
