Enantioselective synthesis of planar-chiral benzosiloloferrocenes by Rh-catalyzed intramolecular C-H silylation.

The first synthesis of planar-chiral benzosiloloferrocenes was achieved by the intramolecular reaction of 2-(dimethylhydrosilyl)arylferrocenes. The enantioselective cross dehydrogenative coupling of an sp(2) C-H bond of ferrocene with a Si-H bond proceeded efficiently with the use of a Rh-chiral diene catalyst.

Iridium-catalyzed enantioselective C-H alkylation of ferrocenes with alkenes using chiral diene ligands.

The first catalytic and enantioselective C-H alkylation of ferrocene derivatives with various alkenes was achieved. A cationic iridium complex, having a chiral diene ligand, and an isoquinolyl moiety as a directing group are essential for regioselective and enantioselective C-H bond activation.

Rh(III)-catalyzed directed C-H bond amidation of ferrocenes with isocyanates.

[RhCp*(OAc)(2)(H(2)O)] [Cp* = pentamethylcyclopentadienyl] catalyzed the C-H bond amidation of ferrocenes possessing directing groups with isocyanates in the presence of 2 equiv/Rh of HBF(4)·OEt(2). A variety of disubstituted ferrocenes were prepared in high yields, or excellent diastereoselectivities.