Formoxyboranes as hydroborane surrogates for the catalytic reduction of carbonyls through transfer hydroboration.

A new class of Lewis base stabilized formoxyboranes demonstrates the feasibility of catalytic transfer hydroboration. In the presence of a ruthenium catalyst, they have shown broad applicability for reducing carbonyl compounds. Various borylated alcohols are obtained in high selectivity and yields up to 99%, tolerating several functional groups. Computational studies enabled to propose a mechanism for this transformation, revealing the role of the ruthenium catalyst and the absence of hydroborane intermediates.

Silyl formates as hydrosilane surrogates for the transfer hydrosilylation of ketones.

A transfer hydrosilylation of ketones employing silyl formates as hydrosilane surrogates under mild conditions is presented. A total of 24 examples of ketones have been successfully converted to their corresponding silyl ethers with 61-99% yields in the presence of a PNHP-based ruthenium catalyst and silyl formate reagent. The crucial role of the ligand for the transformation is demonstrated.

Silylation of O-H bonds by catalytic dehydrogenative and decarboxylative coupling of alcohols with silyl formates.

The silylation of O-H bonds is a useful methodology in organic synthesis and materials science. While this transformation is commonly achieved by reacting alcohols with reactive chlorosilanes or hydrosilanes, we show herein for the first time that silylformates HCO2SiR3 are efficient silylating agents for alcohols, in the presence of a ruthenium molecular catalyst.

Use of the Nosyl Group as a Functional Protecting Group in Applications of a Michael/Smiles Tandem Process.

Concise preparations of elaborated polycyclic and heterocyclic systems present in natural products were obtained using the nosyl group as a functional protecting group not only to mask the reactivity of a sensitive moiety but also to provide a structure desired in the final target. The group is transferred to the substrate during deprotection through a novel extension of the Truce-Smiles rearrangement in tandem with a 1,4-addition. This strategy provides access to a ring system laden with valuable functionalities for subsequent manipulations and can serve as a versatile building block for the construction of more complex molecular architectures such as indoles in a manner compatible with the concepts of green chemistry and atom economy.