Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(9), P. 3146 - 3146
Published: Jan. 1, 2023
Transition-metal-catalyzed
asymmetric
C-H
borylation
is
one
of
the
most
powerful
strategies
for
construction
chiral
organoborate
compounds,
which
has
attracted
extensive
attention
in
fields
synthetic
chemistry,
medicinal
chemistry
and
materials
science
due
to
its
atom-and
step-economy.The
design
synthesis
novel
ligands
are
essential
success
borylation.Based
on
development
ligands,
recent
progress
transition-metal-catalyzed
C(sp
2
)-H
3
reactions
summarized.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 3258 - 3262
Published: April 3, 2024
An
efficient
cobalt-catalyzed
selective
hydroboration
of
1,3-enynes
with
HBpin
toward
1,3-dienylboronate
esters
is
disclosed.
With
a
commercially
available
catalytic
system
Co(acac)2
and
dppf,
the
reactions
proceeded
well
to
afford
wide
range
1,3-dienylborates
in
moderate
high
yields.
This
protocol
features
cheap
base-metal
system,
broad
substrate
scope,
excellent
selectivity,
easy
gram-scale
preparation,
good
functional
group
tolerance
provides
access
synthetically
valuable
1,3-dienylborates.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8888 - 8895
Published: Jan. 1, 2024
A
highly
efficient
method
achieves
precise
construction
of
alkyl
chiral
centers
at
remote
C3-positions
in
five-membered
S/O-heterocycles
via
cobalt-catalyzed
asymmetric
hydroalkylation
heterocyclic
alkenes.
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.
Synlett,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 13, 2025
Abstract
‘Chain-walking’
chemistry,
a
catalytic
process
enabling
the
functionalization
of
remote
positions
in
carbon
chains,
has
traditionally
relied
on
transition-metal
catalysts
to
facilitate
alkene
isomerization
and
subsequent
transformations.
This
Synpacts
article
reviews
recent
advancements
hydroboration
via
chain-walking
pathways,
highlighting
transition-metal-catalyzed
strategies
for
α-,
β-,
terminal-selective
borylation.
Additionally,
organoboron
compounds
emerging
role
borenium
species
as
mimics
are
discussed.
In
particular,
we
highlight
our
work
borenium-catalyzed
‘chain
walking’
functionalization,
where
have
unveiled
novel
metal-free
‘functionalization-then-isomerization’
strategy.
1
Introduction
2
Background
2.1
Transition-Metal-Catalyzed
Remote
Hydroboration
2.2
Isomerization
Organoboron
Compound
2.3
Borenium-Catalyzed
Internal
Alkenes
3
‘Chain
Walking’
3.1
‘Boron-Walking’
Strategy
Design
3.2
Reaction
Scope
3.3
Synthetic
Application
3.4
Mechanistic
Study
4
Summary
Outlook
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 19, 2025
A
novel
and
efficient
dual-catalysis
strategy
using
nickel
palladium
has
been
developed
for
the
cross-coupling
of
halostibines
with
aryl
triflates
to
form
C(sp2)-Sb
bonds.
This
approach
shows
a
wide
substrate
scope
high
functional
group
tolerance
could
be
conducted
on
gram
scale.
The
synthesized
arylstibines
also
arylation
reagents
reacting
alkyl
phenyl
alkenes
olefins
ligands
regulate
hydrogenation
diphenylacetylene.
In
addition,
arylstibine
3q
satisfactory
anticancer
activity
against
cancerous
MDA-MB-231
cells.
JACS Au,
Journal Year:
2024,
Volume and Issue:
4(6), P. 2312 - 2322
Published: June 11, 2024
Enantioenriched
3-methylpyrrolidine,
with
its
unique
chiral
nitrogen-containing
core
skeleton,
exists
widely
in
various
functional
molecules,
including
natural
products,
bioactive
compounds,
and
pharmaceuticals.
Traditional
methods
for
synthesizing
these
valuable
methyl-substituted
heterocycles
often
involve
enzymatic
processes
or
complex
procedures
auxiliaries,
limiting
the
substrate
scope
efficiency.
Efficient
catalytic
methylation,
especially
an
enantioselective
manner,
has
been
a
long-standing
challenge
chemical
synthesis.
Herein,
we
present
novel
approach
remote
stereoselective
installation
of
methyl
group
onto
N-heterocycles,
leveraging
CoH-catalyzed
asymmetric
hydromethylation
strategy.
By
effectively
combining
commercial
cobalt
precursor
modified
bisoxazoline
(BOX)
ligand,
variety
easily
accessible
3-pyrrolines
can
be
converted
to
enantiopure
3-(isotopic
labeling)methylpyrrolidine
compounds
outstanding
enantioselectivity.
This
efficient
protocol
streamlines
two-step
synthesis
enantioenriched
which
previously
required
up
five
six
steps
under
harsh
conditions
expensive
starting
materials.
Radical
chemistry
is
synthetically
useful
but
can
be
plagued
by
the
non-intuitive
reaction
course
and
indiscriminate
reactivity
profile.
Herein,
dynamic
radical
effect
revealed
as
a
conceptual
logic
for
predictive
achievement
of
selectivity.
The
reversible
bonding
association/dissociation
two
radicals
serves
synthetic
handle
directing
one
to
target
recourse,
without
participation
other
radical.
A
Mn
catalytic
protocol
has
been
developed
cycloalkene
ring
expansion
synthesis
azaheterocycles.
An
initial
azidyl
addition
alkene
subsequent
O2
occupation
C-radical
site
prevents
further
coupling
steers
toward
intramolecular
rearrangement
pathway.
broad
substrate
scope
established
pyridine
isoquinoline
derivatives.
This
new
perspective
promises
an
important
guiding
principle
empowering
radical-based
chemical
transformations.
