Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(8)
Опубликована: Окт. 30, 2023
Within
the
sphere
of
traditional
Pd
Язык: Английский
Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units
Lewis McGhie,
Alessandro Marotta,
Patrick O. Loftus
и другие.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15850 - 15859
Опубликована: Май 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
Язык: Английский
Orthogonal sp3‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Фев. 12, 2024
Abstract
In
this
study,
a
series
of
enantioenriched
sp
3
‐Ge/B
bimetallic
modules
were
successfully
synthesized
via
an
enantioselective
copper‐catalyzed
hydroboration
carbagermatrane
(
Ge
)‐containing
alkenes.
Orthogonal
cross‐coupling
selectivity
under
different
Pd‐catalyzed
conditions
was
achieved
in
enantiospecific
manner.
Notably,
the
chiral
secondary
exhibited
remarkable
transmetallation
ability
prior
to
primary
or
Bpin.
The
effectiveness
Ge/B
strategy
further
demonstrated
through
development
new
functional
small
molecules
with
Aggregation‐Induced
Emission
(AIE)
and
Circularly
Polarized
Luminescence
(CPL)
performance.
This
represents
first
successful
example
synthesis
alkylgermanium
reagents
that
permit
reactions.
Язык: Английский
Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21257 - 21263
Опубликована: Июль 26, 2024
Because
of
their
robustness
and
orthogonal
reactivity
features,
alkyl
germanes
bear
significant
potential
as
functional
handles
for
the
construction
C(sp3)-rich
scaffolds,
especially
in
context
modular
synthetic
approaches.
However,
to
date,
only
radical-based
has
been
accessible
from
these
handles,
which
limits
types
possible
decorations.
Here,
we
describe
first
general
C(sp3)–heteroatom
bond
formation
(−GeEt3)
by
leveraging
electrochemistry
unlock
polar
reactivity.
This
approach
allowed
us
couple
C(sp3)–GeEt3
with
a
variety
nucleophiles
construct
ethers,
esters,
amines,
amides,
sulfonamides,
sulfides,
well
C–P,
C–F,
C–C
bonds.
The
compatibility
electrochemical
strategy
C1
motif
was
also
showcased,
involving
sequential
functionalization
Cl,
Bpin,
ultimately
GeEt3
via
electrochemistry.
Язык: Английский
Photoinduced decarboxylative germylation of α-fluoroacrylic acids: Access to germylated monofluoroalkenes
Chemical Communications,
Год журнала:
2024,
Номер
60(51), С. 6556 - 6559
Опубликована: Янв. 1, 2024
Herein,
a
novel
strategy
is
presented
for
the
photoinduced
decarboxylative
and
dehydrogenative
cross-coupling
of
wide
range
α-fluoroacrylic
acids
with
hydrogermanes.
This
methodology
provides
an
efficient
robust
approach
producing
various
germylated
monofluoroalkenes
excellent
stereoselectivity
within
brief
photoirradiation
period.
The
feasibility
this
reaction
has
been
demonstrated
through
gram-scale
reaction,
conversion
monofluoroalkenes,
modification
complex
organic
molecules.
Язык: Английский
Photocatalytic Germylation via Direct Hydrogen Atom Transfer
Wenshan Wang,
Yan Liu,
Qiang Gao
и другие.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 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.
Язык: Английский
Toward Multi‐Functionalized Organogermaniums: Diastereoselective Transformations of Germacycles Derived from Cheletropic Reactions of Boron‐Substituted Butadienes with Ge(II) Salts
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 22, 2024
Abstract
The
field
of
organogermanium
in
chemistry
has
recently
attracted
attention.
Thanks
to
the
inherent
features
germanium
(Ge),
introducing
Ge‐based
substituents
into
organic
frameworks
enhanced
bioactivity
and
optoelectronic
properties
molecules.
Herein,
synthesis
multi‐functionalized
organogermaniums
using
Ge(II)
salts
is
reported.
germacycles
having
an
allylboron
moiety,
which
derived
from
(4+1)
cycloadditions
butadienes
bearing
a
boronic
ester
moiety
with
salts,
can
be
applied
further
allylboration
aldehydes
perfect
diastereoselectivity.
obtained
allylated
adducts
enable
access
π‐extended
retention
stereocenters.
Язык: Английский
Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis
Angewandte Chemie,
Год журнала:
2023,
Номер
136(8)
Опубликована: Окт. 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.
Язык: Английский
Orthogonal sp3‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling
Angewandte Chemie,
Год журнала:
2024,
Номер
136(16)
Опубликована: Фев. 12, 2024
Abstract
In
this
study,
a
series
of
enantioenriched
sp
3
‐Ge/B
bimetallic
modules
were
successfully
synthesized
via
an
enantioselective
copper‐catalyzed
hydroboration
carbagermatrane
(
Ge
)‐containing
alkenes.
Orthogonal
cross‐coupling
selectivity
under
different
Pd‐catalyzed
conditions
was
achieved
in
enantiospecific
manner.
Notably,
the
chiral
secondary
exhibited
remarkable
transmetallation
ability
prior
to
primary
or
Bpin.
The
effectiveness
Ge/B
strategy
further
demonstrated
through
development
new
functional
small
molecules
with
Aggregation‐Induced
Emission
(AIE)
and
Circularly
Polarized
Luminescence
(CPL)
performance.
This
represents
first
successful
example
synthesis
alkylgermanium
reagents
that
permit
reactions.
Язык: Английский
Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 3198 - 3204
Опубликована: Дек. 5, 2024
We
report
the
synthesis
of
germanyl
triazoles
formed
via
a
copper-catalysed
azide-alkyne
cycloaddition
(CuAAC)
alkynes.
The
reaction
is
often
high
yielding,
functional
group
tolerant,
and
compatible
with
complex
molecules.
installation
Ge
moiety
enables
further
diversification
triazole
products,
including
chemoselective
transition
metal-catalysed
cross-coupling
reactions
using
bifunctional
boryl/germyl
species.
Язык: Английский