Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(11), P. 1901 - 1906
Published: March 9, 2023
A
nickel-catalyzed
enantio-
and
regioconvergent
alkylation
of
regioisomeric
mixtures
racemic
germylated
allylic
electrophiles
with
alkyl
nucleophiles
is
reported.
Key
to
success
a
newly
developed
hept-4-yl-substituted
Pybox
ligand
that
enables
accessing
various
chiral
γ-germyl
α-alkyl
building
blocks
in
excellent
yields
enantioselectivities.
The
reason
for
the
regioconvergence
steering
effect
bulky
germyl
group.
resulting
vinyl
germanes
can
be
easily
halodegermylated
without
racemization
stereocenter
afford
synthetically
valuable
γ-stereogenic
halides.
Chemistry of Materials,
Journal Year:
2022,
Volume and Issue:
34(12), P. 5726 - 5739
Published: June 9, 2022
Covalent
organic
frameworks
(COFs)
are
an
emerging
class
of
crystalline
porous
materials
with
tailor-made
functionalities
for
improved
photocatalytic
activity.
However,
limited
choice
building
blocks
greatly
restricts
the
photochemical
performance
and
application
scope
COFs
in
photocatalysis.
Herein,
a
covalent
hybridization
approach
is
reported
to
address
these
issues
by
knitting
rigid
macrocyclic
struts,
namely,
pillararenes,
into
extended
network
COFs.
Varying
different
ratios
pillararenes
unique
conformations
electron-rich
cavities
can
not
only
generate
confined
molecular
space
exciton
migration
carrier
transport
but
also
create
new
interfaces
interplay
photogenerated
charge
carriers,
leading
high
promoting
efficient
oxidation
amines
imines.
This
work
paves
way
constructing
macrocycle-derived
provides
promising
platform
photocatalysis
through
predesign
functionalization
pore
surface.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(23), P. 15850 - 15859
Published: May 28, 2024
Light-driven
strategies
that
enable
the
chemoselective
activation
of
a
specific
bond
in
multifunctional
systems
are
comparatively
underexplored
comparison
to
transition-metal-based
technologies,
yet
desirable
when
considering
controlled
exploration
chemical
space.
With
current
drive
discover
next-generation
therapeutics,
reaction
design
enables
strategic
incorporation
an
sp3
carbon
center,
containing
multiple
synthetic
handles
for
subsequent
space
would
be
highly
enabling.
Here,
we
describe
photoactivation
ambiphilic
C1
units
generate
α-bimetalloid
radicals
using
only
Lewis
base
and
light
source
directly
activate
C–I
bond.
Interception
these
transient
with
various
SOMOphiles
rapid
synthesis
organic
scaffolds
(B,
Si,
Ge)
orthogonal
activation.
In-depth
theoretical
mechanistic
studies
reveal
prominent
role
2,6-lutidine
forming
photoactive
charge
transfer
complex
stabilizing
situ
generated
iodine
radicals,
as
well
influential
boron
p-orbital
activation/weakening
This
simple
efficient
methodology
enabled
expedient
access
functionalized
3D
frameworks
can
further
derivatized
available
technologies
C–B
C–Si
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(4), P. 2664 - 2670
Published: Feb. 6, 2024
A
light-driven
method
for
the
generation
of
aryl
radicals
from
triarylbismuth(III)
and
(V)
reagents
is
described.
Aryl
radical
proposed
to
occur
through
ligand-assisted
mesolytic
cleavage
an
organobismuth(IV)
intermediate
generated
either
oxidation
BiIII
or
reduction
BiV.
This
mode
demonstrated
be
compatible
with
a
range
bimolecular
arylations,
including
hydroarylation
electron-deficient
olefins
arylation
diboronates,
disulfides,
sulfonyl
cyanides,
phosphites,
isocyanides.
The
intermediacy
supported
by
trapping
clock
experiments,
BiIV–aryl
mesolysis
computationally.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(22), P. 3063 - 3081
Published: June 10, 2023
Comprehensive
Summary
Hydrogermylation
of
alkenes
and
alkynes
provides
a
straightforward
synthetic
route
to
organogermanium
compounds
that
have
been
found
applications
in
organic
synthesis,
medicinal
chemistry,
material
science.
This
paper
reviews
the
advances
transition‐metal‐catalyzed
hydrogermylation
unsaturated
carbon‐carbon
bonds,
including
alkenes,
alkynes,
dienes,
allenes,
with
objective
providing
readers
status
field.
Progress,
problems,
perspectives
this
field
are
discussed.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 4109 - 4118
Published: Feb. 13, 2023
A
catalytic
approach
of
synthesizing
the
cis-selective
saturated
carbo-
and
heterocyclic
germanium
compounds
(3D
framework)
is
reported
via
hydrogenation
readily
accessible
aromatic
germanes
(2D
framework).
Among
numerous
catalysts
tested,
Nishimura's
catalyst
(Rh2O3/PtO2·H2O)
exhibited
best
reactivity
with
an
isolated
yield
up
to
96%.
broad
range
substrates
including
synthesis
unprecedented
was
explored.
This
selective
strategy
could
tolerate
several
functional
groups
such
as
−CF3,
−OR,
−F,
−Bpin,
−SiR3
groups.
The
synthesized
products
demonstrated
applications
in
coupling
reactions
newly
developed
aza-Giese-type
addition
reaction
(C–N
bond
formation)
from
cyclic
germane
product.
These
versatile
motifs
can
have
a
substantial
value
organic
medicinal
chemistry
they
show
orthogonal
while
competing
other
partners
boranes
or
silanes,
acquiring
three-dimensional
structure
high
stability
robustness.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
A
1,1-hydroboration
of
alkynylgermanes
with
unique
trans-Ge/B
stereochemistry
under
transition-metal-free
conditions
is
reported.
Mechanistic
studies
suggest
that
a
pathway
involving
α-boration
followed
by
stepwise
1,2-Ge/H
shift
on
the
intermediate
structurally
lies
between
an
alkyne-Ge+
π
complex
and
typical
vinyl
cation.
The
resulting
Ge/B
bimetallic
modules,
along
Ge*/Ge/B
trimetallic
variant,
can
be
conveniently
transformed
into
trisubstituted
olefins
through
iterative
divergent
cross-coupling.
This
work
demonstrates
incorporating
metalloids
classical
organic
reactions
may
offer
unconventional
chemical
selectivity
efficient
synthetic
applications.
Synthesis,
Journal Year:
2023,
Volume and Issue:
55(11), P. 1792 - 1798
Published: Feb. 15, 2023
Abstract
The
direct
hydrogermylation
of
alkenes
under
Lewis
acid
catalysis
is
reported.
use
borane
B(C6F5)3
as
a
catalyst
allows
for
mild,
metal-free
and
concomitant
reduction
ketones
aldehydes.
Regardless
electronic
biases,
anti-Markovnikov
observed
in
high
yields.
Moreover,
the
process
scalable
proceeds
mild
conditions
at
room
temperature.