ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
15(1), P. 63 - 71
Published: Dec. 13, 2024
The
development
of
synthetic
methods
for
the
selective
installation
methyl
and
fluoromethyl
groups
is
highly
desired
due
to
their
critical
role
in
drug
development.
While
significant
advances
have
been
made
methylation
difluoromethylation
aromatic
compounds,
catalytic
atroposelective
(fluoro)methylative
functionalization
alkynes
forge
axially
chiral
alkenes
remains
underexploited.
Herein,
we
report
an
enantioselective
cross-electrophile
strategy
efficient
1,2-carbo-(fluoro)methylation
with
two
different
alkyl
halides
via
nickel
catalysis.
By
integrating
a
one-electron
radical
process
two-electron
organometallic
process,
this
protocol
employs
simple
catalyst
effectively
discriminate
between
secondary
tertiary
(fluoro)methyl
alkyne
difunctionalization.
This
demonstrates
good
compatibility
activated
secondary/tertiary
bromides,
terminal
alkynes,
halides,
permitting
straightforward
synthesis
broad
range
synthetically
valuable
(fluoro)methyl-substituted
high
chemo-,
regio-,
trans-,
atropo-selectivity.
Preliminary
mechanistic
studies
provide
insight
into
potential
reaction
pathway.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(47), P. 32283 - 32291
Published: Nov. 13, 2024
Compounds
bearing
both
boryl
and
amino
groups
at
distal
positions
are
invaluable
synthons
for
synthesizing
pharmaceuticals,
drug
candidates,
natural
products,
but
their
catalytic
enantioselective
synthesis
remains
rarely
explored.
We
report
the
first
1,4-borylamination
reaction
through
a
copper-catalyzed
cascade
hydroborylation
hydroamination
of
arylidenecyclopropanes.
This
combines
four
readily
available
components
in
highly
chemo-,
site-,
fashion
(>20:1
r.r.
up
to
99%
ee),
yielding
diverse
array
synthetically
valuable
enantioenriched
4-amino
alkylboronates.
The
versatile
utility
these
products
is
highlighted
by
transformations
wide
applications
pharmaceutical
discovery.
Preliminary
mechanistic
studies
were
conducted
elucidate
operative
pathway,
intermediates,
origins
its
high
chemo-
site-selectivity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
A
three-component
cascade
boronation–dearomatization
reaction
of
alkenes,
a
diboron
compound,
and
pyridinium
salt
is
diclosed,
affording
chiral
boron-containing
1,4-dihyropyridines
in
high
yields
(≤98%)
diastereoselectivity
(≤10:1
dr),
along
with
excellent
enantioselectivity
(typically
>99%
ee).
The
catalytic
system
performs
efficiently
at
low
catalyst
loadings
(1
mol
%)
was
tested
>50
examples,
including
some
biologically
active
molecules.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 20, 2025
A
palladium-catalyzed
three-component
1,3-dienylation
of
propargylic
esters
with
DABSO
and
aryl
iodides
has
been
developed.
This
novel
reductive
cross-coupling
reaction
produces
2-sufonylated
1,3-dienes
as
single
products
in
the
presence
metal
Mn
high
regio-
chemoselectivities.
Control
experiments
demonstrated
that
transformation
may
undergo
a
radical
process.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Abstract
Palladium‐catalyzed
cross
coupling
of
enolates—α‐arylation—is
an
established
method
for
chemical
synthesis.
A
major
challenge
in
the
field
is
control
stereochemistry
α‐carbon.
This
typically
due
to
facile
epimerization
under
basic
reaction
conditions
α‐arylation.
In
this
study,
alternative
approach
presented
that
involves
Pd/Cu‐catalyzed
arylboration
electron
deficient
alkenes.
The
products
are
generated
with
high
levels
diastereoselectivity
a
broad
range
substitution
patterns.
Enantioselective
variants
also
addition
product
derivatizations.
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Abstract
Palladium‐catalyzed
cross
coupling
of
enolates—α‐arylation—is
an
established
method
for
chemical
synthesis.
A
major
challenge
in
the
field
is
control
stereochemistry
α‐carbon.
This
typically
due
to
facile
epimerization
under
basic
reaction
conditions
α‐arylation.
In
this
study,
alternative
approach
presented
that
involves
Pd/Cu‐catalyzed
arylboration
electron
deficient
alkenes.
The
products
are
generated
with
high
levels
diastereoselectivity
a
broad
range
substitution
patterns.
Enantioselective
variants
also
addition
product
derivatizations.
Synlett,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 9, 2025
Abstract
Compounds
bearing
both
boryl
and
amino
groups
are
highly
valuable
synthons
in
organic
synthesis.
However,
while
enantioselective
1,1-
1,2-borylamination
reactions
have
been
developed,
processes
enabling
distal
borylamination
rarely
investigated.
Here,
we
present
an
1,4-borylamination
reaction,
achieved
through
a
copper-catalyzed
cascade
hydroborylation
hydroamination
of
arylidenecyclopropanes.
This
four-component
reaction
provides
direct
access
to
enantioenriched
4-aminoalkylboronate
products
with
high
chemo-,
site-,
enantioselectivity.
The
versatility
these
was
demonstrated
their
broad
transformations
extensive
applications
the
synthesis
various
drug
core
structures.
Additionally,
preliminary
mechanistic
studies
were
conducted
investigate
pathway,
intermediates,
chemo-
site-selectivity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 7, 2025
A
photoinduced
radical
arylboration
of
unactivated
alkenes
with
B2pin2
and
aryl
nitriles
was
developed,
providing
a
mild
efficient
approach
to
access
useful
β-aryl
boronates
in
the
absence
transition-metal
catalyst.
This
reaction
undergoes
boron
addition
alkene
subsequent
radical-radical
coupling
process.
showcases
good
functional
group
compatibility
provides
promising
complementary
strategy
chemistry
traditional
transition-metal-catalyzed
coupling.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 10, 2025
Multiboronated
compounds
play
more
and
significant
roles
in
the
chemical
community,
1,1,1-triborylalkanes
have
emerged
as
versatile
building
blocks
organic
synthesis.
However,
efficient
strategies
for
assembly
of
such
are
very
rare.
A
general
atom-economical
synthesis
from
various
alkenes
with
pinacolborane
(HBpin)
is
reported
first
time.
The
success
this
transformation
relies
on
use
commercially
available
Schwartz
reagent
(Cp2ZrHCl)
a
catalyst,
enabling
sequential
dehydrogenative
borylation
hydroboration.
This
reaction
demonstrates
excellent
selectivity,
high
yields,
broad
functional
group
tolerance.
Mechanistic
investigations
reveal
that
process
begins
two
consecutive
borylations
catalyzed
by
zirconium,
producing
1,1-diborylalkene
intermediate,
which
subsequently
undergoes
hydroboration
HBpin
to
afford
1,1,1-triborylalkanes.
Notably,
approach
allows
remote
1,1,1-triboration
internal
alkenes.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
palladium-catalyzed
stereospecific
ring-opening
arylation
of
α-aminoaryl-tethered
alkylidenecyclopropanes
for
the
stereoselective
synthesis
1,1,2-trisubstituted
conjugated
dienes
has
been
developed.