A
class
of
C2-symmetrical
bisoxazoline
ligands
with
a
flexible
chiral
pocket
has
been
developed,
which
could
be
readily
prepared
in
three
steps
from
enantiopure
SPSiOLs.
This
type
presented
high
level
enantioselectivity
for
the
Cu-catalyzed
asymmetric
carbene
insertion
Ge–H
bonds
α-trifluoromethyl
diazo
compounds,
thus
providing
an
efficient
method
preparation
enantioenriched
ogranogermanes.
reac-tion
features
broad
substrates
scope,
mild
reaction
conditions,
excellent
enantioselectivity,
and
low
catalyst
loading.
Preliminary
mechanistic
studies
un-veiled
that
this
might
undergo
concerted
mechanism,
computational
unveiled
origin
induction
SPSiBox
ligand.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 28, 2025
Here,
we
report
the
Cu-catalyzed
asymmetric
carbene
insertion
into
both
Ge-H
and
Si-H
bonds
with
α-trifluoromethyl
diazo
compounds,
enabled
by
a
class
of
newly
developed
C2-symmetrical
bisoxazoline
ligands.
This
protocol
provides
an
efficient
method
for
preparation
enantioenriched
ogranogermanes
organosilanes,
featuring
broad
substrate
scope,
mild
reaction
conditions,
excellent
enantioselectivity,
low
catalyst
loading.
The
key
to
tolerance
is
use
SPSiBox
ligands
bearing
flexible
tunable
chiral
pocket.
Preliminary
mechanistic
studies
computational
unveiled
origin
induction
ligands,
mechanism
insertion.
not
only
new
construction
trifluoromethyl-containing
molecules
but
also
opens
avenue
Si-
Ge-containing
functional
molecules.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 9, 2025
An
iridium-catalyzed
asymmetric
allylic
substitution
with
sequential
boron
incorporation
is
reported.
The
reaction
accommodates
a
wide
range
of
substrates,
affording
chiral
N,O-bidentate
difluoroboron
complexes
in
excellent
yields
high
enantioselectivities.
Furthermore,
decigram-scale
reaction,
synthetic
transformations,
as
well
photophysical
property
investigations
the
are
explored.
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.
A
class
of
C2-symmetrical
bisoxazoline
ligands
with
a
flexible
chiral
pocket
has
been
developed,
which
could
be
readily
prepared
in
three
steps
from
enantiopure
SPSiOLs.
This
type
presented
high
level
enantioselectivity
for
the
Cu-catalyzed
asymmetric
carbene
insertion
Ge–H
bonds
α-trifluoromethyl
diazo
compounds,
thus
providing
an
efficient
method
preparation
enantioenriched
ogranogermanes.
reac-tion
features
broad
substrates
scope,
mild
reaction
conditions,
excellent
enantioselectivity,
and
low
catalyst
loading.
Preliminary
mechanistic
studies
un-veiled
that
this
might
undergo
concerted
mechanism,
computational
unveiled
origin
induction
SPSiBox
ligand.
