Parts of the mechanistic studies, detailed experimental procedures, characterization data, and copies of 1 H and 13 C NMR spectra for new compounds (PDF)
Reductive cross-coupling provides
facile access to organogermanes,
but it remains largely unexplored. Herein we report a nickel-catalyzed
reductive Csp3–Ge coupling of alkyl bromides with
chlorogermanes. This work has established a new method for producing
alkylgermanes. The reaction proceeds under very mild conditions and
tolerates various functionalities including ether, alcohol, alkene,
nitrile, amine, ester, phosphonates, amides, ketone, and aldehyde.
The application of this method to the modification of bioactive molecules
is demonstrated.
Catalytic, three-component, cross-electrophile reactions have recently emerged as a promising tool for molecular diversification, but studies have focused mainly on the alkyl-carbonations of alkenes. Herein, the scope of this method has been extended to conjugated dienes and silicon chemistry through silylative difunctionalization of 1,3-dienes with chlorosilanes and aryl bromides. The reaction proceeds under mild conditions to afford 1,2-linear-silylated products, a selectivity that is different to those obtained from conventional methods via an intermediary of H(C)-η 3 -π-allylmetal species. Preliminary mechanistic studies reveal that chlorosilane reacts with 1,3-diene first and then couples with aryl bromide.
Transition-metal-catalyzed
sila-cycloaddition has been a promising
tool for accessing silacarbocycle derivatives, but the approach has
been limited to a selection of well-defined sila-synthons. Herein,
we demonstrate the potential of chlorosilanes, which are industrial
feedstock chemicals, for this type of reaction under reductive nickel
catalysis. This work extends the scope of reductive coupling from
carbocycle to silacarbocycle synthesis and from single C–Si
bond formation to sila-cycloaddition reactions. The reaction proceeds
under mild conditions and shows good substrate scope and functionality
tolerance, and it offers new access to silacyclopent-3-enes and spiro
silacarbocycles. The optical properties of several spiro dithienosiloles
as well as structural variations of the products are demonstrated.
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