A Vinyl Cyclopropane Ring Expansion and Iridium-Catalyzed Hydrogen Borrowing Cascade.

A vinyl cyclopropane rearrangement embedded in an iridium-catalyzed hydrogen borrowing reaction enabled the formation of substituted stereo-defined cyclopentanes from Ph* methyl ketone and cyclopropyl alcohols. Mechanistic studies provide evidence for the ring-expansion reaction being the result of a cascade based on oxidation of the cyclopropyl alcohols, followed by aldol condensation with the pentamethyl phenyl-substituted ketone to form an enone containing the vinyl cyclopropane. Subsequent single electron transfer (SET) to this system initiates a rearrangement, and the catalytic cycle is completed by reduction of the new enone. This process allows for the efficient formation of diversely substituted cyclopentanes as well as the construction of complex bicyclic carbon skeletons containing up to four contiguous stereocentres, all with high diastereoselectivity.

A Tethered Ru-S Complex with an Axial Chiral Thiolate Ligand for Cooperative Si-H Bond Activation: Application to Enantioselective Imine Reduction.

An axial chiral version of the 2,6-dimesitylphenyl group attached to sulfur is reported. Its multistep preparation starts from (S)-binol, and the thiol group is established by a racemization-free thermal Newman-Kwart rearrangement. The new chiral thiolate ligand decorated with one mesityl group is used in the synthesis of a tethered ruthenium chloride complex. Its spectroscopic characterization revealed solvent-dependent epimerization at the ruthenium center. The major diastereomer is crystallographically characterized. Chloride abstraction with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4 ) yields the corresponding coordinatively unsaturated ruthenium complex with the Ru-S bond exposed. Si-H bond activation at this Ru-S bond proceeds in syn fashion but with moderate facial selectivity (d.r.=70:30), generating diastereomeric chiral-at-ruthenium hydrosilane adducts. Their application to catalytic imine hydrosilylation led to promising enantioinduction (40 % ee), thereby providing proof of concept for asymmetric catalysis involving cooperative Si-H bond activation.

Catalytic Electrophilic C-H Silylation of Pyridines Enabled by Temporary Dearomatization.

A CH silylation of pyridines that seemingly proceeds through electrophilic aromatic substitution (SE Ar) is reported. Reactions of 2- and 3-substituted pyridines with hydrosilanes in the presence of a catalyst that splits the SiH bond into a hydride and a silicon electrophile yield the corresponding 5-silylated pyridines. This formal silylation of an aromatic CH bond is the result of a three-step sequence, consisting of a pyridine hydrosilylation, a dehydrogenative CH silylation of the intermediate enamine, and a 1,4-dihydropyridine retro-hydrosilylation. The key intermediates were detected by (1) H NMR spectroscopy and prepared through the individual steps. This complex interplay of electrophilic silylation, hydride transfer, and proton abstraction is promoted by a single catalyst.