Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(22), P. 4618 - 4633
Published: Oct. 16, 2024
Abstract
Germanium
(Ge),
a
congener
of
carbon,
possesses
unique
properties
that
hold
extensive
potential
for
applications
across
multiple
domains.
Recent
years
have
seen
significant
progress
in
the
development
carbon‐germanium
bond
formation
strategies,
particularly
those
more
challenging
C(
sp
3
)−Ge
bonds.
This
review
systematically
summarizes
recent
advances
forming
methodologies,
with
particular
emphasis
on
(1)
versatility
transition‐metals,
including
iron,
nickel,
copper,
rhodium
and
palladium,
as
catalysts
broadening
reaction
scope
controlling
selectivity;
(2)
powerfulness
organic
photocatalysis
achieving
mild
selective
formation,
(3)
sustainability
catalytic
electrosynthesis
facilitating
chemical
oxidant‐/reductant‐
free
conversions.
Additionally,
examples
(4)
non‐catalytic
strategies
are
also
discussed.
The
representative
scopes,
well
mechanistic
proposals,
these
protocols
highlighted.
Through
an
overview
current
state
research,
this
aims
to
offer
insights
into
construction
bonds,
provide
perspectives
future
research
directions
address
challenges.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(17), P. 2405 - 2408
Published: Jan. 1, 2024
Nickel-catalysed
chelation-assisted
reductive
cross-coupling
of
trifluoropropanamides/esters
with
disulfides
to
afford
thioacrylamides/esters
high
E
selectivity,
involving
triple
C–F
bond
cleavage.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 28, 2025
Alkylating
bismuthanes
containing
C(sp3)-Bi
bonds
were
first
disclosed
as
early
1850,
but
their
development
remains
severely
limited,
especially
the
synthetic
method.
Herein,
we
developed
Fe/Mn-synergistic
promoted
cross-coupling
of
alkyl
halides
with
chlorobismuthanes,
which
can
access
alkylbismuthanes
in
satisfactory
yields
various
functional
group
compatibility
(cyano,
ester,
aldehyde,
and
amide).
Inactivated
chlorides/bromides,
well
cyclic
acyclic
electrophiles,
smoothly
yielded
corresponding
products.
Gram-scale
synthesis
late-stage
modification
drug
molecules
also
conducted.
The
synthesized
could
be
alkylation
reagents
toward
C(sp3)-C(sp2),
C(sp3)-Se,
C(sp3)-S,
C(sp3)-N
bonds.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12848 - 12852
Published: Aug. 15, 2024
We
describe
a
visible
light-induced
palladium-catalyzed
radical
germylative
arylation
of
alkenes
with
easily
accessible
chlorogermanes.
This
protocol
provides
expedient
access
to
germanium-substituted
indolin-2-ones
in
good
excellent
yields
under
mild
reaction
conditions.
The
key
step
for
this
strategy
lies
the
reductive
activation
germanium–chloride
bonds
an
excited
palladium
complex
light
irradiation.
involvement
germanium
radicals
was
evidenced
by
electron
paramagnetic
resonance
spectroscopy
experiments.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(21), P. 15623 - 15629
Published: Oct. 9, 2024
We
have
developed
a
visible-light-induced
method
to
photolyze
digermanes
through
single-electron
oxidation
using
photocatalyst,
in
contrast
direct
excitation,
generate
germyl
radicals
and
achieve
the
hydro/deuteriogermylation
of
alkenes.
This
protocol
allows
previously
elusive
incorporation
small
trimethylgermyl
group
deuterium,
metabolically
stable
bioisosteres
tert-butyl
hydrogen,
respectively,
making
this
approach
attractive
not
only
organic
synthesis
but
also
medicinal
chemistry.
