Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
136(8)
Published: Oct. 30, 2023
Abstract
Within
the
sphere
of
traditional
Pd
0
/Pd
II
cross
coupling
reactions,
organogermanes
have
been
historically
outperformed
both
in
terms
scope
and
reactivity
by
more
conventional
transmetalating
reagents.
Subsequently,
this
class
compounds
has
largely
underutilized
as
a
partner
bond‐forming
strategies.
Most
recent
studies,
however,
shown
that
alternative
modes
activation
these
notoriously
robust
building
blocks
transform
into
most
reactive
site
molecule—capable
outcompeting
other
functional
groups
(such
boronic
acids,
esters
silanes)
for
C−C
C–heteroatom
bond
formation.
As
result,
over
past
few
years,
literature
increasingly
featured
methodologies
explore
potential
chemoselective
orthogonal
partners.
Herein
we
highlight
some
advances
field
organogermane
chemistry
with
respect
to
their
synthesis
applications
synthetic
catalytic
transformations.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(41)
Published: May 8, 2024
Abstract
We
have
established
a
facile
and
efficient
protocol
for
the
generation
of
germyl
radicals
by
employing
photo‐excited
electron
transfer
(ET)
in
an
donor‐acceptor
(EDA)
complex
to
drive
hydrogen‐atom
(HAT)
from
hydride
(R
3
GeH).
Using
catalytic
amount
EDA
commercially
available
thiol
benzophenone
derivatives,
ET‐HAT
cycle
smoothly
proceeds
simply
upon
blue‐light
irradiation
without
any
transition
metal
or
photocatalyst.
This
also
affords
silyl
radical
hydride.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 2150 - 2157
Published: Jan. 22, 2025
This
study
reports
the
development
of
a
photocatalytic
germanyl
functionalization
unactivated
olefins.
A
modular
approach
to
alkylgermanium
trihalides
was
realized
through
three-component
radical
reaction
involving
fluoroalkyl
bromides
and
commercially
available
GeBr2
in
redox-neutral
process.
The
target
organogermanes
were
readily
obtained
via
one-pot
derivatization
using
various
Grignard
reagents,
demonstrating
good
functional
group
compatibility
with
amides,
esters
ketones.
work
highlights
utility
Ge(II)
reagents
constructing
C–Ge
bonds
photoredox
catalysis.
Notably,
selectivity
capturing
electrophilic
or
nucleophilic
radicals
by
found
be
significantly
influenced
halide
ligands
on
GeX2.
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
Comprehensive
Summary
An
innovative
visible‐light‐driven
direct
hydrogen
atom
transfer
(
d
‐HAT)
of
Ge–H
bond
has
been
developed,
wherein
the
photoexcited
9,10‐phenanthraquinone
PC
HAT
9
)
serves
as
an
efficient
photocatalyst
for
generation
germanium‐centered
radicals
from
germanium
hydrides
including
Ph
3
GeH,
n
Bu
and
2
GeH
.
By
employing
hypervalent
iodine
reagents
SOMOphiles,
this
protocol
facilitates
streamlined
germylation
through
a
mechanism
involving
germyl
radical
addition
followed
by
β‐cleavage
carboxyl
to
yield
diverse
array
ethynyl‐,
vinyl‐,
nitrile‐,
phenyl‐functionalized
germanes.
The
methodological
leap
signifies
noteworthy
departure
previous
photocatalytic
indirect
i
relying
on
combined
usage
SET
with
abstractors,
which
not
only
advances
methodology
creating
in
fashion
but
also
provides
access
structurally
novel
pharmaceutically
promising
organogermanium
compounds
that
are
difficult
synthesize
routine
methods.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(18)
Published: Feb. 7, 2024
Abstract
Rh(II)
porphyrin
complexes
display
pronounced
metal‐centered
radical
character
and
the
ability
to
activate
small
molecules
under
mild
conditions,
but
catalysis
with
porphyrins
is
extremely
rare.
In
addition
facile
dimerization,
readily
engage
in
kinetically
thermodynamically
reactions
involving
two
centers
generate
stable
Rh(III)−X
intermediates
that
obstruct
turnover
thermal
catalysis.
Here
we
report
site
isolation
of
metalloradicals
a
MOF
host,
which
not
only
protects
against
also
allows
them
participate
Access
PCN‐224
or
PCN‐222
linkers
are
fully
metalated
by
absence
any
accompanying
Rh(0)
nanoparticles
was
achieved
via
first
direct
synthesis
linker
containing
transition‐metal
alkyl
moiety,
followed
Rh(III)−C
bond
photolysis.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(11), P. 7899 - 7912
Published: May 10, 2024
An
efficient,
practical,
and
metal-free
protocol
for
the
synthesis
of
silicon-containing
isoindolin-1-ones
deuterated
analogues
via
synergistic
combination
an
organic
photoredox
hydrogen
atom
transfer
process
is
described.
This
strategy
features
mild
reaction
conditions,
high
economy,
excellent
functional
group
compatibility,
delivering
a
myriad
structurally
diverse
valuable
products
with
good
to
yields.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
13(4)
Published: Dec. 23, 2023
Abstract
Hydrogen‐atom
transfer
(HAT)
catalysis
offers
an
atom‐
and
step‐economical
approach
to
the
direct
functionalization
of
aliphatic
C−H
bonds.
While
structure
HAT
catalysts
largely
affects
reactivity
selectivity
in
step
where
bond
is
cleaved,
choice
viable
for
from
strong
bonds
limited.
The
recent
development
organic
based
on
flexibly
modifiable
molecular
platform
has
enabled
fine‐tuning
steric
electronic
properties
these
catalysts,
thus
greatly
expanding
their
structural
diversity.
This
review
focuses
design
with
cationic
moieties
as
common
motifs
application
selective
manipulation
challenging
substrates,
including
unactivated
hydrocarbons.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(13)
Published: May 11, 2023
Abstract
The
light‐promoted
regioselective
germylation
of
aryl
propiolamides/alkynoates
with
germanium
hydrides
is
reported.
germyl‐containing
spiro[4.5]trienones
were
obtained
when
N
‐arylpropiolamides
used
via
sequential
C−Ge
and
C−C
bond
formation,
while
alkynoates
delivered
the
vinylgermanes
radical
Smiles
rearrangement
CO
2
release.
