Streamlining Si-O bond formation through cobalt-catalyzed dehydrocoupling.

Herein we report a strategy for the synthesis of organosilicons, including siloxanes, silyl ethers, and aminosilanes, via Co-catalyzed dehydrogenative coupling between hydrosilanes and nucleophiles. This discovery represents an expansion of the synthetic toolkit for organosilicon synthesis, forging Si-O and Si-N bonds in the presence of cobalt complexes with salen-type ligands.

Cobalt-Catalyzed Reduction of Aldehydes to Alcohols via the Hydroboration Reaction.

A method for the reduction of aldehydes with pinacolborane catalyzed by pincer cobalt complexes based on a triazine backbone is developed in this paper. The presented methodology allows for the transformation of several aldehydes bearing a wide range of electron-withdrawing and electron-donating groups under mild conditions. The presented procedure allows for the direct one-step hydrolysis of the obtained intermediates to the corresponding primary alcohols. A plausible reaction mechanism is proposed.

Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species.

The reactions between silanols or terminal acetylenes with alkynylgermanes have been accomplished using potassium bis(trimethylsilyl)amide as the catalyst. This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such as KOH can serve as efficient catalysts in this process.

B(C6F5)3-Catalyzed Dehydrocoupling of POSS Silanols with Hydrosilanes: A Metal-Free Strategy for Effecting Functionalization of Silsesquioxanes.

We report a highly effective metal-free catalytic procedure for the functionalization of silsesquioxanes via dehydrocoupling of various POSS silanols with hydrosilanes in the presence of commercially available tris(pentafluorophenyl)borane B(C6F5)3. This approach enables the unprecedented one-pot synthesis of valuable silsesquioxane derivatives under mild conditions, with no corrosive byproducts formed in the process.

Ru-Catalyzed Dehydrogenative Silylation of POSS-Silanols with Hydrosilanes: Its Introduction to One-Pot Synthesis.

A commercially available and stable ruthenium dodecacarbonyl catalyst (Ru3(CO)12) allows very efficient and convenient access to functionalized silsesquioxanes (SQs) containing siloxane moiety (Si-O-Si) via dehydrogenative coupling of POSS-silanols with hydrosilanes. With the aid of SiH-containing silsesquioxanes, an unprecedented one-pot procedure has been revealed, and the usefulness of this approach was demonstrated by the synthesis of various derivatives via O-silylation, as well as C═C and C═N hydrosilylation.