Angewandte Chemie,
Год журнала:
2023,
Номер
135(43)
Опубликована: Сен. 12, 2023
Abstract
Reported
herein
is
a
fully
orthogonal
olefination,
which
involves
the
site‐
and
E‐selective
coupling
of
aryl
germanes
with
alkenes,
tolerating
otherwise
widely
employed
handles
such
as
aromatic
(pseudo)halogens
(C−I,
C−Br,
C−Cl,
C−F,
C−OTf,
C−OSO
2
F),
silanes
boronic
acid
derivatives
well
alternative
functionalities.
This
unprecedented
[Ge]‐based
oxidative
Heck
proceeds
at
room
temperature
high
speed
(10
min
to
hours)
operational
simplicity
owing
its
base‐free
air‐tolerant
features.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3278 - 3286
Опубликована: Фев. 15, 2024
Herein,
we
reported
the
enantioconvergent
Csp3–Csp2
cross-coupling
reaction
with
1,4-dihydropyridine
(DHP)
derivatives
via
photoredox/nickel
dual
catalysis
to
access
chiral
products
good
yield
and
enantioselectivity.
The
operationally
simple
was
carried
out
under
mild
conditions
functional
group
tolerance.
Due
use
of
a
stoichiometric
equivalent
aryl/alkenyl
halides
as
coupling
partners,
sequential
iterative
synthesis
could
be
achieved
smoothly
in
one
pot
for
position
isomers
stereoisomers.
In
proposed
mechanism,
kinetic
experiments
mechanistic
studies
indicated
that
radical
generation,
depended
on
excited
photocatalyst
DHP,
rate-determining
step.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Фев. 22, 2024
Abstract
We
report
the
triply
selective
and
sequential
diversification
of
a
single
C
sp
3
carbon
carrying
Cl,
Bpin
GeEt
for
modular
programmable
construction
‐rich
molecules.
Various
functionalizations
−Cl
−BPin
(e.g.
alkylation,
arylation,
homologation,
amination,
hydroxylation)
were
tolerated
by
−GeEt
group.
Moreover,
methodological
repertoire
alkyl
germane
functionalization
was
significantly
expanded
beyond
hitherto
known
Giese
addition
arylation
to
alkynylation,
alkenylation,
cyanation,
halogenation,
azidation,
C−S
bond
formation
as
well
first
demonstration
stereo‐selective
‐[Ge]
bond.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(43)
Опубликована: Сен. 12, 2023
Reported
herein
is
a
fully
orthogonal
olefination,
which
involves
the
site-
and
E-selective
coupling
of
aryl
germanes
with
alkenes,
tolerating
otherwise
widely
employed
handles
such
as
aromatic
(pseudo)halogens
(C-I,
C-Br,
C-Cl,
C-F,
C-OTf,
C-OSO2
F),
silanes
boronic
acid
derivatives
well
alternative
functionalities.
This
unprecedented
[Ge]-based
oxidative
Heck
proceeds
at
room
temperature
high
speed
(10
min
to
2
hours)
operational
simplicity
owing
its
base-free
air-tolerant
features.
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.
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.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(45)
Опубликована: Май 8, 2024
Demonstrated
here
is
an
external
photo-sensitizer-free
(auto-sensitized)
singlet
oxygen-enabled
solvent-dependent
tertiary
hydroxylation
and
aryl-alkyl
spiro-etherification
of
C3-maleimidated
quinoxalines.
Such
"reagent-less"
photo-oxygenation
at
Csp
